CM Punk's heel turn against Jeff Hardy immediately came to mind -- but that might be because I was just in the CM Punk thread. But I did love the turn. When Punk cashed in Money in the Bank against Jeff Hardy, there was fan backlash, but that was just because Hardy was popular. Punk had every right to cash in the case as he did, and even Good Ol' JR was on his side. He didn't turn heel right away. It simmered, and then when he nailed Jeff Hardy with the microphone? BAM! That was so unexpected and the beat-down that followed was really quite vicious for WWE standards. Since then, Punk has never looked back.
Also, The Undertaker turning in 2001 got me. I was a much younger fan at the time, and seeing a big good guy come down to the ring to defend a helpless announcer from a self-righteous heel boss like Vince McMahon was what I had been conditioned to see. Then "Do you think you're better than me, JR?" At that moment, before he even struck helpless JR, the heel turn was in place. Just those words, followed by JR's shocked "Oh no! I don't!" face. Vince being surprised also helped. It was like he got a free pass from the devil to do whatever he wanted.
When thinking of face turns, it's hard to really come up with one -- but the Batista one is a great example. I marked out like a little bitch when it happened, as did pretty much everyone here, regardless of if they admit it. Batista got really stale really fast as a babyface, but everything leading up to that moment (and thereafter) was perfect.
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