Would love to give this to Vanille, but I've not actually played FFXIII. Instead I've heard and seen her by proxy and damn, she's right up there. Mr Potato Head from Hasbro Family Game Night was a highly placed contestant but he's so bad I don't think he deserves any more attention. It's got to be:

Oddjob - Goldeneye - N64

I know he's not an NPC but he's probably induced more rage in me than any other video game character ever. He is about two-feet shorter than everyone else in the game, meaning that fire would fly harmlessly over his head while the smug bastard that picked him shot my knees off. In the time before proper FPS controls on consoles, picking Oddjob was basically cheating. This t-shirt exists for a reason:

To everyone that thought playing him was fine, I hate you. So much.