I'm not that much of a super villain type, but if I were to pick, I would relate to Doctor Doom from The Avengers or Doctor Willy from Mega Man, because I have the creative mind of both of them, even if I'm a girl. Hero side: Iron Man, because I LOVE the ability to create stuff to help people :)
If I were a villain I'd relate most with Loki because I know what it's like to be rejected and disapproved of. Not meaning to sound like a whiney punk or anything (:. If I were a hero I'd relate with Captain America not because I'm tough or anything but I don't like bullying and I try to do what's right.
If I was to be a super hero. It would be wonder woman because I brought both my children up alone from 6 & 7 weeks old & worked 3 jobs x 60 hours a week for 6 years. it was my courage that was my strength, & when you combine courage & strength you find faith. Not faith in the lord but faith in yourself to do whatever is necessary to keep your family safe, well & with a roof over their head. If I had a bad day then I probably felt like Witchipoo off HR Puffinstuff. She never got the golden flute no matter how hard she tried.
Probably the pointy-nose-old-guy from Despicable Me. Or Doofenshmirtz. Because at the time when I feel like I'm doing something naughty or smart, a year or so later I just look back and realize it was pathetic.