#1 Randy Orton and Edge
By the time Edge and Randy Orton paired up to take on a reformed DX in 2006, they had both been world champions in WWE. Edge, in particular, had just lost his WWE Championship to John Cena shortly before forming Rated-RKO with The Viper.
Triple H and Shawn Michaels needed some top-level heels to feud with, after easing past the Spirit Squad among others. Edge and Orton were the perfect fit for that team, giving DX one hell of a feud.
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It was a pretty inspired pairing, with both men in their prime in the ring and their shared cocky aggression that was easy to hate. Rated-RKO handed DX their first loss since reuniting that year but would suffer humiliation at Survivor Series.
Their 5-man team was swept by a star-studded Team DX, including the likes of CM Punk and the Hardy Boyz. Edge and Orton won the World Tag Team Championship along the way, further intensifying this feud, which was supposed to end at New Year's Revolution.
However, Triple H blew out his quad during the match and had to miss months of action. As a result, WWE quickly decided to have John Cena step in and help Shawn Michaels topple Edge and Orton. Following that, both Superstars would end up turning on each other by WrestleMania 23, where they faced off in the Money in the Bank Ladder Match.
Rated-RKO could have been a truly special and memorable team, but Hunter's injury along with the lack of long-term planning prevented it from happening.