Little Mac is pretty much guaranteed - He got an AT last game and has now gotten a franchise revival. Others that are very likely due to the same reasons are Saki Amamiya and Isaac. I'm expecting all of those three, to be honest.
Besides that, I think we can expect somebody from The Last Story, if it becomes a hit like I hope. I'd want King K. Rool in it, but apparently Nintendo don't want him in so yeah. I think, in general, we can expect a lot of characters from new franchises or franchises that have grown. Mario, for example, already has every important character from the series in the game. Same goes for Zelda and Kirby. So I think it'd be more aimed towards new/revived franchises than before.