IMO, the best mic workers I've ever seen are, in no particular order:
1) The Rock - Charisma, humor, seriousness, the ability to ad-lib make him one of, if not the, best mic worker I've ever seen. When he became "The Rock," he put more emotion and sarcasm into his promos and interviews than anyone I've ever seen. The bits he did with Kevin "Hermie" Kelly were hilarious. He had so many catch phrases and inventive bits, and when he made fun of other wrestlers it was truly hilarious. I don't know how much of his promos were scripted, but I truly believe he went off on his own tangents sometimes and the higher-ups saw that he was gold and just let him go.
2) "Macho Man" Randy Savage - IMO, one of the best all-around professional wrestlers to ever step foot in a ring. But we're talking about mic skills here, and he definitely had those. He always seemed wired, and the fact that he stressed words at weird times made it that much more funny. When I watched his promos, I seriously thought he was gonna have a heart attack at any moment. The exchanges he had with Mean Gene Okerlund in backstage stand-ups were golden.
3) "Stone Cold" Steve Austin - While a lot of people didn't like Austin, he knew how to captivate an audience. He was the guy that everyone related to, doing what everyone wanted to do (get back at a boss who treated him like crap). Back when he was "Stunning Steve" Austin, his promos sucked. When he first became "Stone Cold," however, everything changed. He portrayed great anger in his promos and later moved to the more crowd-interactive stuff. His "What?" line is still used today when heels do promos in the ring. That's a sign that you were a great mic worker.
4) The Ultimate Warrior - Let's face it, The Artist Formerly Known As Jim Helwig gave us some of the greatest (albeit it comedic) moments on the mic. I was actually watching a lot of old UW promos today. Yeah, you needed a translator for his stuff, but the emotion he put into it was priceless. He would make up stuff off the top of his head, and the crazy talk fit perfectly into the character. In that era of pro wrestling, he was one of the best in using stand-ups and promos to develop his character. Whenever I need a pick-me up, I bring up one of his promos and it makes me laugh.
5. Mick Foley - The Master of Cheap Pop. Even back when he was Cactus Jack and a heel Mankind, he gave some interesting interviews and promos. Mick is a ham. He mugs for the camera whenever he can. The Mankind character really gave him more of an ability to speak and work the crowd. He's cheesy, loves the cheap pop and knows it.
6. "Rowdy" Roddy Piper - Let's face it, Piper was one of the first real controversial wrestlers because of his mouth. He just berated everyone. He put great emotion and thought into the majority of his promos (sans the "drunk" promo he did with Bret Hart). Piper was never a great in-ring talent. His expertise was always as a mouthpiece. I always considered him the Don Rickles of pro wrestling.
7. Ric Flair - For years and years, he was the cocky guy everyone hated, but you had to respect the fact that the Nature Boy was gold on the mic. He portrayed the "limousine-riding, jet-flying, wheeling, dealing, kiss-stealing son of a gun" attitude like no other. You looked at the guy and just hated him because he had the appearance of the rich playboy you wished you could be. A lot of his angles put him as the high-and-mighty cocky bastard against the common man (Dusty Rhodes, Ricky Steamboat, et al). And on the occasions when he went nuts, he really looked and talked like he should have been in a padded room. Flair made you believe he was an asshole. Plus, who else has a signature line that's being used almost 30 years since he started using it? WHOOOOOO!
There are a few others I'd consider as honorable mentions, including Ted DiBiase Sr., Road Warrior Hawk, J.J. Dillon, Paul Heyman and even Vince McMahon.