Phoenix debuted on WWE's main roster on the May 8, 2006 episode of Raw as a face by attacking Mickie James while James was assaulting Trish Stratus. After this incident, James berated Phoenix for "ruining everything" and questioned why she showed up in the first place. A week later, Phoenix was formally introduced by Stratus and then attacked a distracted James on Stratus's behalf. When James finally escaped, Phoenix claimed that James had "ruined her life", and would not let her get away with it, before calling her a "psycho". On the following episode of Raw, Phoenix attacked James after her match with Torrie Wilson. Then, on the May 29 episode of Raw, Phoenix and Wilson, with Stratus in their corner, teamed together to defeat Candice Michelle and Victoria, who had James in their corner. During the June 5 episode of Raw, Phoenix suffered a legitimately fractured mandible during a match with Victoria, but was able to continue the match, and emerged victorious despite the injury. She spent a year having surgeries and recovering, including getting a titanium plate and nine screws placed in her jaw.
On the July 9, 2007, episode of Raw, Phoenix returned as a villain, when Melina claimed to be injured. Phoenix replaced Melina in a tag team match as Jillian Hall's partner, and the two lost to Candice Michelle and Mickie James. At the SummerSlam pay-per-view, Phoenix won the Interpromotional Divas battle royal to become the number one contender for Michelle's WWE Women's Championship. Phoenix was then pushed as a dominating Diva, dubbing herself "The Glamazon" and attacking James, Hall, and Michelle on the September 10 episode of Raw. At Unforgiven, however, she failed to capture the Women's Championship from Michelle. Their storyline rivalry continued when Phoenix pinned Michelle during a non-title mixed tag team match on Raw on September 24.
At No Mercy in October, Phoenix defeated Michelle to win her first WWE Women's Championship. She retained the title on the October 22 episode of Raw in a two out of three falls match, in which Candice Michelle was injured by Phoenix shaking the rope, causing her to fall off the top turnbuckle and legitimately break her clavicle.
During a 10-Diva tag team match at Survivor Series, Phoenix's team lost after Melina was pinned by Mickie James. On the November 26 episode of Raw, James defeated Melina in a number one contenders match for Phoenix's Women's Championship, setting up a title match between the two at Armageddon, a match in which Phoenix successfully defended her Women's title. On New Year's Eve 2007, Phoenix successfully defended her title in a Triple Threat match against Melina and James, after pinning Melina.
Phoenix, along with then-ally Melina, took part in the Playboy BunnyMania Lumberjack match at WrestleMania XXIV, where she defeated the team of Ashley and Maria. On April 14, 2008 Phoenix faced Mickie James with her Women's Championship on the line and lost, ending her reign as champion. Phoenix received a rematch on the May 5 episode of Raw in a lumberjill match, but lost after Melina unintentionally hit her in the face with her boot. On the May 12 episode of Raw, Melina and Phoenix partnered to face Maria and James. During the match, Melina unintentionally knocked Phoenix off of the ring apron, resulting in Phoenix abandoning Melina, which allowed James and Maria to pick up the win. Later that night, Melina and Phoenix brawled in a backstage segment, ending their alliance. At Judgment Day, Phoenix failed to regain the Women's Championship in a Triple Threat match after James pinned Melina to retain the title. At One Night Stand, Phoenix defeated Melina in the first women's "I Quit" match in WWE history. The next night on Raw, Phoenix teamed with Katie Lea Burchill to defeat Melina and James in a tag team match. She was pinned by James one week later in a non-title match, and was once again attacked by Melina post-match.
After a month absence from television, Phoenix returned on the July 14 episode of Raw, where she defeated Santino Marella after he issued an open challenge to any WWE wrestler backstage. The storyline continued the following week after Marella lost to the returning D-Lo Brown. Phoenix confronted Marella after the match, and they briefly grappled with each other before unexpectedly sharing a kiss, to which both expressed considerable confusion.
The two then became an on-screen power couple, and the pairing of Phoenix and Marella later became known by the portmanteau Glamarella. Within the team, she acted as the "straight-woman" of sorts, berating Marella or reacting in disbelief to his over-the-top, embarrassing antics. At SummerSlam, they defeated Kofi Kingston and Mickie James in an intergender tag team match. Phoenix pinned James, winning the Women's Championship, while Marella won Kingston's Intercontinental Championship. She successfully defended the Women's Championship against Candice Michelle at No Mercy. At Survivor Series in November, Phoenix was team captain of the victorious Raw Diva team which defeated the SmackDown Divas in a five-on-five elimination match; she eliminated Maryse and became the sole survivor of the team.
On December 8, 2008, Phoenix received the "Slammy Award" for Diva of the Year. Phoenix then began feuding with Melina, who had returned from injury in November. This storyline included the debut of Rosa Mendes, who was introduced as Phoenix's "superfan". At the Royal Rumble in January 2009, Phoenix lost the Women's Championship to Melina. At WrestleMania XXV, Phoenix competed in the 25-Diva "Miss WrestleMania" battle royal; despite scoring 12 eliminations, more than any other participant, she lost when Marella, who competed in drag, claiming to be his twin sister "Santina", last eliminated her. After WrestleMania, Glamarella separated, as Phoenix was unhappy with Santino pretending to be "Santina". Phoenix had a brief scripted rivalry with both "Santina" and Marella, and challenged "Santina" for the "Miss WrestleMania" title at Backlash, but was unsuccessful.
After a brief hiatus, Phoenix returned on the July 27 episode of Raw, teaming with Alicia Fox and Rosa Mendes in a losing effort to Mickie James, Gail Kim, and Kelly Kelly. Phoenix had her first opportunity for the WWE Divas Championship, being narrowly defeated by the defending champion, Mickie James, on the August 31 episode of Raw, after winning a number one contender's battle royal that same night.
On the October 12 episode of Raw, it was announced that Phoenix had been traded to the SmackDown brand. Phoenix made her in-ring debut for the brand on the October 30 episode of SmackDown, defeating Jenny Brooks, an enhancement talent. In January 2010, at the Royal Rumble, she entered the Royal Rumble match and eliminated The Great Khali, before she was eliminated by CM Punk. With her entry, she became the second woman in history to enter the Royal Rumble match, the first being Chyna.
After being told by Vickie Guerrero, the SmackDown consultant, that she would not be receiving a Women's Championship opportunity, Phoenix turned face after she saved Tiffany from an attack by Guerrero and LayCool (Michelle McCool and Layla) on the March 12 episode of SmackDown. She then went on to defeat McCool and Layla in a tag team match involving Tiffany. The feud with McCool continued at WrestleMania XXVI, where they were on opposing teams in a 10-Diva tag team match, which Phoenix's team lost, although they won a rematch the following night on Raw. On the April 23 episode of SmackDown, Phoenix teamed with Mickie James to face McCool and Layla. After the match, LayCool beat down Phoenix and smeared make-up on her face and body while she was unconscious. This resulted in Phoenix receiving a match for the Women's Championship against McCool at Extreme Rules, where she defeated McCool in an "Extreme Makeover" match to win her third Women's Championship. On the May 6 episode of Superstars, Phoenix tore her ACL in a match against Rosa Mendes, and as a result, one week later on SmackDown, McCool invoked her rematch clause to face Phoenix in a two-on-one handicap match along with Layla, where Layla pinned Phoenix to become the new Women's Champion.
Phoenix returned from her injury at November's Survivor Series pay-per-view, and attacked the former co-Champions Michelle McCool and Layla, after they lost the WWE Divas Championship to Natalya. Phoenix and Natalya then formed an alliance, and at TLC: Tables, Ladders & Chairs in December, Phoenix and Natalya defeated LayCool in the first Divas Tag Team Tables match in WWE history.
As part of the 2011 Supplemental Draft on April 26, 2011, Phoenix returned to the Raw brand. On the August 1 episode of Raw, Phoenix won a battle royal to become the number one contender to the WWE Divas Championship, and afterward attacked champion Kelly Kelly to provoke a feud and turning heel in the process. Phoenix later declared that she was tired of the "perky bimbos" that comprised the rest of the Divas division, and was on a mission to make a mockery of the other Divas, and was joined by Natalya to form The Divas of Doom. Phoenix went on to unsuccessfully challenge Kelly for the championship at SummerSlam. Throughout September, The Divas of Doom feuded with Kelly and Eve Torres on Raw and The Chickbusters (AJ and Kaitlyn) on SmackDown. Phoenix challenged Kelly for the Divas Championship again at Night of Champions, but was unsuccessful. At Hell in a Cell in October, Phoenix defeated Kelly to win the Divas Championship for the first time, with help from Natalya. In a rematch on the October 14 episode of SmackDown, Phoenix successfully retained the championship. At Vengeance, Phoenix successfully defended the championship against Eve Torres, with both Natalya and Kelly banned from ringside. Phoenix successfully retained her championship against Torres again at Survivor Series on November 20 in a lumberjill match, and against Kelly at TLC: Tables, Ladders & Chairs on December 18.
Further successful defenses followed against Torres on the January 30, 2012, episode of Raw and Tamina Snuka at Elimination Chamber on February 19. After this, Phoenix competed only sporadically for a few months, including a tag team match at WrestleMania XXVIII, where she and Eve Torres were defeated by Kelly Kelly and Maria Menounos. On the April 6 episode of SmackDown, Phoenix lost to Nikki Bella in a non-title match, following Kelly's interference. On the April 23 episode of Raw, Phoenix lost her Divas Championship to Nikki Bella in a lumberjill match, after suffering a storyline ankle injury. At Extreme Rules, Phoenix was scheduled to face Nikki in a rematch for the Divas Championship, however she was not medically cleared to compete and was replaced by the returning Layla, who ended up winning the title. Phoenix made two unsuccessful attempts at regaining the Divas Championship from Layla at Over the Limit in May and at No Way Out in June, respectively.
In September, Kaitlyn was attacked by an unknown assailant prior to her championship match at Night of Champions. Upon her return, she announced her assailant had blonde hair, and Assistant SmackDown General Manager Eve Torres accused Phoenix before attacking her. On the September 28 episode of SmackDown, after defeating Natalya, Phoenix was suspended by Torres, but the suspension was later reversed by SmackDown general manager Booker T. On the October 1 episode of Raw, Phoenix lost to Torres. Phoenix turned heel again on the October 18 episode of Superstars, when she berated Kaitlyn for thinking that Phoenix attacked her and demanded respect from Kaitlyn, before losing to her in a singles match. On the October 29 episode of Raw, Phoenix was defeated by AJ Lee in a singles match, but the match was restarted by Raw Managing Supervisor Vickie Guerrero, allowing Phoenix to win. After the match, in storyline, Guerrero fired Phoenix for her poor performance, therefore Phoenix left WWE.
On February 27, 2017, WWE announced that Phoenix would be inducted into the WWE Hall of Fame. Her induction made her the quickest female to be inducted after her retirement, as she had retired only five years prior, and made her and her husband Edge the first real-life couple to both be inducted.
Starting in 2018, Phoenix became a part-time color commentator for WWE, mainly for women-related events, starting from January 16 to April 3, 2018 for the first season of the WWE Mixed Match Challenge, commenting the tournament each week alongside Michael Cole and Corey Graves. On January 28, 2018 at the Royal Rumble event, she made a one-night wrestling return as a face for the first time since 2012 by entering the first-ever women's Royal Rumble match as a competitor, making her the first person to appear in both a men's and women's Royal Rumble. She entered at number 24 and lasted over two minutes before being eliminated by Natalya.
Phoenix went on to continue to work as a guest commentator at various events and mainly women's matches such as: the WrestleMania Women's Battle Royal at WrestleMania 34, the 2018 Mae Young Classic, the women's Royal Rumble match at the 2019 Royal Rumble event, and the Elimination Chamber match to determine the inaugural WWE Women's Tag Team Champions at the 2019 Elimination Chamber event.
On March 10, 2019, at the Fastlane pay-per-view, Phoenix acted as commentator on the WWE Women's Tag Team Championship match between defending champions The Boss 'n' Hug Connection (Bayley and Sasha Banks) and Nia Jax and Tamina. After their defeat, Jax and Tamina attacked Bayley and Banks; Phoenix came to their aid, soon joined by Natalya, but the four were still overpowered by Jax and Tamina. The following day on Raw, Phoenix accompanied Natalya to her match against Jax, eventually causing a disqualification by attacking Jax.
On the March 18, 2019 episode of Raw, Phoenix announced that she was coming out of retirement; she and Natalya reformed their 2011–2012 tag team The Divas of Doom, and challenged The Boss 'n' Hug Connection for a WWE Women's Tag Team Championship match at WrestleMania 35; however, Tamina ambushed Phoenix after a distraction from Jax during a one-on-one match between Natalya and Banks. On the April 1 episode of Raw, Phoenix wrestled her first match in nearly seven years, where she teamed with Natalya, Bayley and Banks, to face off against Jax, Tamina, and The IIconics (Billie Kay and Peyton Royce), where Phoenix's team emerged victorious after she pinned Royce following a Glam Slam. At WrestleMania, Phoenix and Natalya lost to The IIconics during a fatal four-way tag team match for the Women's Tag Team Championship, when, after Phoenix performed a Glam Slam from the second rope on defending champion Bayley without realizing that The IIconics' Billie Kay had tagged Phoenix out, was thrown outside the ring by Kay's partner Peyton Royce, who allowed Kay to successfully pin Bayley.
On May 15, 2019, Phoenix joined the commentary team of NXT alongside Mauro Ranallo and Nigel McGuinness, replacing Percy Watson; this marked her first time as full-time commentator, and her first time commenting matches that did not involve women. Her first NXT TakeOver as announcer was NXT TakeOver: XXV on June 1, 2019.
Phoenix returned to the ring for the first time since the previous year's WrestleMania during the Women's Royal Rumble match at the 2020 Royal Rumble event, entering at number 19 and lasting over 23 minutes before being eliminated by Shayna Baszler, finishing in third place (her personal best Rumble performance for in-ring time and final rank). She sufferred a head injury early in the match when Bianca Belair slapped her chest and caused the back of Phoenix's neck to hit one of the ring posts around the ring, but was able to finish the match.
On the March 2 episode of Raw, Phoenix would make an appearance, to provide a medical update on her husband Edge (who had made his in-ring return during the previous Men's Royal Rumble match, and incidentally finished in third place like Phoenix did in the Women's), who was kayfabe injured by Randy Orton. However, Orton would interrupt and explain his actions, which caused Phoenix to slap and kick Orton, who retaliated by hitting her with an RKO.
At WWE Day 1, Phoenix returned to help her husband Edge clinch the win against The Miz. This then led to a mixed tag team match at the Royal Rumble, where she and Edge defeated The Miz and Maryse. On the August 22 episode of Raw, Phoenix returned to watch Edge's match against Damian Priest. After the match, The Judgment Day (Priest, Finn Bálor and Rhea Ripley) attacked Edge, but Phoenix stepped in to stop the assault. She then interfered in Edge's "I Quit" match against Bálor at Extreme Rules, but despite her heroic efforts, Edge ultimately lost. After he said "I Quit", Rhea Ripley attacked Phoenix with a con-chair-to, severely injuring her.
In 2023, Phoenix returned at the Royal Rumble, spearing Ripley before walking off with Edge.