The first thing that came to my mind was Batman, it could be cool to have a live-action Sherlock-Holmes meets Bruce Lee meets Bill Gates.
I know Barry Allen is going to be on CW's "Arrow" alas, I haven't watched a single episode yet.
I'd like to see more Live-action shows with bigger names, I think with Marvel and DC going with movies and merchandising they could pump a lil more money into the television industry. It's less $$$ though..
I would LOVE a Doctor Doom movie/show. They could really break the bank if they start doing Super-villain movies/shows.
My favorite villain thus far (casting wise) has to be Michael Fassbender as Magneto, edging out Tom Hiddleson as Loki. But fit like a glove.