There's a couple that spring to mind:

Vanessa of P.N.03. Though I put the hate on this game something fierce, the game did have its own sense of style. And it's ass wiggling main character is pretty iconic to me, if not to the gaming public as a whole. I don't think I'll soon forget her nonchalant finger snapping as she dispenses laser death to her robotic foes.

And Rio of Lifeline, a game that was maligned by just about everyone BUT me. They really inserted a lot of extraneous material into the game, and did a lot of work on stuff like facial expressions and silly things that the average player might not see. A little futzing around with the menu would reveal dozens of questions you could ask Rio (how do you feel about the prime minister?) and get a heartfelt response that, by-golly, almost felt like you were getting it from a human being. The chick from "She Spies!" did a pretty decent job with the voice acting, which helped.

Playing a little fast and loose with your concept, I know, but that's what I think of...