Burke debuted for WWE on SmackDown! on July 28, 2006, working a mixed martial arts cornerman gimmick with the also debuting Sylvester Terkay. His first WWE match saw him defeating Scott Wright and he would also break Vito's four month winning streak while on SmackDown!, albeit with Terkay's assistance.
On November 7, 2006, Burke and Terkay debuted on the ECW brand by cutting a backstage promo. The following week, Burke replaced Tazz, who had knee surgery, as color commentator alongside play-by-play announcer Joey Styles. Two weeks later, Burke returned to the ring; he and Terkay lost to The Hardys. At the ECW brand's December to Dismember pay-per-view, Burke and Terkay defeated The Full Blooded Italians. The pair were later dubbed The Knock-Out/Tap-Out Connection. On January 18, 2007, Terkay was released from WWE.
Following this, Burke usually wrestled in singles matches, and appeared in a segment where WWE owner Vince McMahon showed disdain for members of the original ECW and called Burke to the ring, naming him "The Future of ECW". Burke was then attacked by Tommy Dreamer, Rob Van Dam, Sabu, and The Sandman, who would later form the ECW Originals stable. Burke then became the official leader of The New Breed, a group of new ECW stars including Matt Striker, Marcus Cor Von and Kevin Thorn, who proceeded to feud with the ECW Originals. At WrestleMania 23, The New Breed faced off against the ECW Originals but were ultimately defeated.
After several weeks of trying to recruit fellow roster mate and new ECW superstar CM Punk, Burke and the New Breed were successful on April 10. Just two weeks later, however, CM Punk betrayed the New Breed, attacking Burke after a match. The next week, Kevin Thorn quit the New Breed due to lack of interference in his match with CM Punk. The same night, Matt Striker and Marcus Cor Von were defeated by the debuting Major Brothers. After being pinned, Burke screamed at Striker creating tension between the two. The New Breed would then feud with the ECW Originals, CM Punk and the Major Brothers at the same time. At Judgment Day, Burke was defeated by CM Punk. Then, at One Night Stand, Burke, Marcus Cor Von and Matt Striker were defeated by Tommy Dreamer, The Sandman and CM Punk in a tables match, ending the New Breed stable.
On June 19, 2007, Burke lost to Chris Benoit (which would be Benoit's last match before his death) in a match that would decide who would face either CM Punk or Marcus Cor Von for the vacant ECW World Championship at Vengeance: Night of Champions. Burke then lost to Punk in a two out of three falls match, which would see the winner becoming the number-one contender to Johnny Nitro's ECW World Championship. On July 10, Burke rebounded with a decisive victory over Balls Mahoney. He was then named the number one contender for the ECW Championship and went on to face CM Punk at the Unforgiven pay-per-view where he was beaten after Punk cleanly pinned him.
Two days later on ECW, an elimination chase was set up by ECW General Manager Armando Estrada. This challenge was to determine the number one contender to CM Punk's ECW Championship in order to compete for the title at No Mercy 2007. Estrada pitted four ECW wrestlers (Burke, Kevin Thorn, Tommy Dreamer and Stevie Richards) against each other in a fatal four-way that night, which Burke won, removing the loser of the match, Richards, from contention. The following week Thorn was eliminated and in the final match of the elimination chase, Burke was eliminated by Dreamer.
Towards the end of 2007, Burke had a short feud with then-World Heavyweight Champion Batista after Batista claimed his upcoming match with Burke was the last thing on his mind, thus disrespecting him and leading to two singles matches against Batista with Burke on the losing end of both. On the November 20 episode of ECW, Burke introduced and formed an alliance with the newest member of the ECW roster, Shelton Benjamin, who moved over from the Raw brand. Burke was then taken off television for several months but he later reappeared by participating in the 2008 Royal Rumble, entering as the 28th entrant, but was eliminated by Triple H after having Mick Foley pushed into him, after which both Foley and Burke were eliminated.
He later participated in a 24-man battle royal at WrestleMania XXIV to determine who would face ECW Champion Chavo Guerrero. Burke was eliminated early in the match (shortly after he himself eliminated Stevie Richards) by Kane. Burke then reappeared again in a tag team match on SmackDown where he and Shelton Benjamin faced Kofi Kingston and then-United States Champion Matt Hardy in a losing effort. Burke faced Hardy the following week in what would be his final televised match, but was unsuccessful. Burke later resurfaced once again in 2008 with a new "Black Pope" gimmick defeating Stevie Richards, Kung Fu Naki and Jamie Noble in dark matches.
On November 10, 2008, Burke was released from his WWE contract after being absent from television since May 2008.