I really doubt we would see anyone that is already too established in a third-party fighting. Cool people like Ryu or Terry Bogard or Kasumi wouldn't make mostly since a good developer wouldn't want to see the characters changed too much from their established forms. (Plus, Nintendo would want Zelda or Samus being their hottest character in the game, not Kasumi).
You also have too look at it as one character per third-party company. Rock/MegaMan would be a good bet from Capcom since he is their main mascot, very popular, and would have a good skill set that would be adapted to the game. Sure he has been in the Marvel vs Capcom games, but he wasn't as prominant a star of that series. (Personally, I would prefer Zero, but to each their own).
If Megaman doesn't get Capcom in, Resident Evil might be another bet. The recent release of Nintendo-only games helps the case for one of their characters migating. This would be an outside chance given that the Blue Bomber would be a better choice, but it is an option that should not be overlooked.
Another good bet might be someone from the Golden Sun series. Great series. Great fan-base. Large array of characters. Established on the GBA. You can probably develop a pretty good character from the material. Best of all, if they exclude Golden Sun, we can have Christopher storm the developer and lay seige to them
Finally, I will put US$100 on the table right now that Square Enix will not get any character from any of their series in SSBB. A lot of them would be cool to have beat the heck out of Mario and Pikachu. A lot of fans would love to see it. I just doubt that SE would send one of their characters to be used like this.
(Oi, I feel like such a loser for putting too much thought into this.)
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