Mueller signed a 3 year deal with World Wrestling Entertainment in July, 2005. On August 22, 2005 a promo was shown showcasing Rhodes' debut along with the returning Lance Cade. He was repackaged as Trevor Murdoch (the surname coming from his likeness to wrestling legend Dick Murdoch), and the team was simply known as Cade and Murdoch. Cade, playing a smooth-talking cowboy, while Murdoch appeared to be an angry southern trucker.
Cade and Murdoch won their debut match on the on September 5, 2005 episode of Raw. They defeated World Tag Team Champions Hurricane and Rosey in a non-title match, themselves a title match at Unforgiven 2005. During the match, Murdoch delivered an Elevated DDT on The Hurricane to the outside, causing The Hurricane to suffer a stinger. This allowed Cade and Murdoch to win the World Tag Team Championship. They would eventually lose their title at Taboo Tuesday 2005 to the Big Show and Kane.
On November 28, 2005 during his match against Shelton Benjamin, commentator Joey Styles acknowledged that Murdoch and Lance Cade were no longer a tag team. It was revealed on WWE Unlimited, that Trevor Murdoch set his sights on Ric Flair and the WWE Intercontinental Championship. On Unlimited, Murdoch had been reviewing movies that were, at the time, playing in theaters, such as Brokeback Mountain, King Kong, and Hostel. The first two movie reviews displayed various sexual habits, while the third showed cruelty in his past. The underlying point of all the reviews that Murdoch was trying to convey is that he believes "city folk" have quite an easy life, as opposed to his.
After breaking up with Cade, he wrestled in singles competition on Heat, normally winning most of his matches while still making small appearances on Raw. He would also have a short feud with The Heart Throbs on Heat which involved him defeating both of them in singles action and gaining a spot in the 2006 Royal Rumble, though he did not win. He then moved on to a short feud with Goldust but was unsuccessful in beating him. He would then feud with both Goldust and his tag partner Snitsky. This led to him helping former partner Cade win his matches and hinted at the two of them reforming their team.
Cade and Murdoch later reformed their tag team, with Cade having a new look with long jet black hair. On the September 4, edition of Raw, Murdoch and Cade lost a number one contender's match for the World Tag Team Title at Unforgiven 2006. The Highlanders won the match when they pinned Charlie Haas who was teamed with Viscera. Murdoch and Cade then joined forces with Edge to oppose D-Generation X (Triple H and Shawn Michaels).
Cade and Murdoch began a feud in April with World Tag Team Champions The Hardys, leading to their title match at Backlash 2007, which The Hardys won. Cade and Murdoch suddenly gained a great deal of respect for The Hardys and began to praise their abilities. The Hardys then began an alliance with Cade and Murdoch. Despite the alliance, Cade and Murdoch faced The Hardys in a rematch at Judgment Day which The Hardys won. On the June 4, edition of Raw, Cade and Murdoch were given another shot at the World Tag Team Championship against The Hardys. Cade and Murdoch were finally successful, becoming two time World Tag Team Champions. When Cade made the pin on Jeff Hardy, Hardy's foot was on the ropes but was pushed off by Murdoch. After the match, when Matt Hardy argued with Cade and Murdoch, they attacked Matt and Jeff with the tag belts, becoming heel once again. They successfully defended their titles against The Hardys at Vengeance: Night of Champions after Cade pinned Jeff and claimed they retained their belts "all by the rules". After that Cade and Murdoch was appeared on Raw and Heat in matches against London and Kendrick, The Highlanders, and Cryme Tyme. On July 23, on Raw, Cade and Murdoch teamed up with Umaga to face John Cena and Candice in a Champions-only handicap tag team match. During the match, Cade and Murdoch trapped Candice in order to set her up for Umaga to attack, until Jeff Hardy came out and attacked Umaga with a steel chair. After Candice left scared, and Umaga gone, Cade & Murdoch were left to square off against John Cena. But Cena defeated them when he threw Cade out of the ring and gave Murdoch an FU. Murdoch, along with Cade lost the titles at a house show on September 5, 2007 to Paul London and Brian Kendrick, but beat them to take the titles back on the last day of the tour. Murdoch and Cade remained champions until the Raw XV Anniversary show, losing the World Tag Team Championships to the team of Hardcore Holly and Cody Rhodes.
Late in April 2008, Murdoch began to develop a country singing gimmick. On the May 12, 2008 edition of Raw, Cade turned on Murdoch following a "victory song," punching Murdoch in the face twice, ending the partnership. The two faced off on the June 2, 2008 edition of Raw, with Cade getting the victory.
As part of the 2008 WWE Supplemental Draft, Murdoch was drafted to the SmackDown brand but he was released from his WWE contract on July 3, 2008 before his debut.