Link. He's the good guy, and when properly characterized (though characterization is always sparse) he's badass. The Hero of Winds is by far my favorite, but the Hero of Time is a close runner-up. Conjure up a Link like that, with a bit more depth, and I'll be even more interested; however, I don't think there are many other Zelda characters I respect enough to actually want to play as them.
Although...I actually liked Kafei quite a bit. He was another determined hero character, but had a bit more depth than Link. I wouldn't mind playing as him, though I have no idea how they'd work a game around him. Komali's a character I actually
can see being the star of the game. Once he matured, he was a much better character.
I don't really like villains so...I don't see the appeal of playing as them, especially since it would be hard to do anything heroic. And if they did work in heroic deeds, it would eliminate the point of them being villains, which would diminish the heros' accomplishments. People seem to fantasize about playing as villains, but why would anyone want to be evil?
Because the Triforce of Courage gives you no obvious ability.
Isn't that one of the better things about Link? I really hate the anime cliche of characters with over-the-top attacks; it works in some JRPGs, but I always liked the fact that Link, though some kind of "chosen one," really seems just like a regular guy who gradually builds his strength. I would think it's much less interesting to play as someone with godlike powers, because hero's journey stories are generally much more compelling and
human. Then again, over-the-top powers are the type of things that have turned me off to the Star Wars prequels, DBZ, etc. so maybe I just don't have the temperament to appreciate those types of characters.
Oddly enough, Okami made playing as a goddess very compelling, but I doubt "destroying worlds" with reckless abandon would even approach the grace and beauty of a title like Okami.