#1 Dean Ambrose vs. Brian Pillman
Some may think that Dean Ambrose vs. Stone Cold Steve Austin would be a great feud/match, which it would, but can you imagine the "Loose Cannon" vs. the "Lunatic Fringe"?
To be perfectly honest, their characters are two of the most similar that anyone could imagine. If Dean Ambrose was in WWF/WWE during the Attitude Era, he would take his persona the extra step or extra mile to go over the edge and take things too far. That is exactly what Brian Pillman was allowed to do with the freedom that his era provided him.
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Ambrose is right there on the verge of losing it at times, but the PG era forces him to be more humorous and not as dangerous. Given more wiggle room, it would not be out of the question to see Dean pull a gun on someone, like Pillman did on Austin back in 1996.
It's difficult to think of a match that could bring about a more entertaining build-up or match than Pillman vs. Ambrose.