They're taking the Tekken 6 approach when it comes to characters. You can start using your favorites day one :]
Also, confirmation of more than 1 single-player mode.
http://blog.us.playstation.com/2012/08/14/playstation-all-stars-gamescom-reveal-dante-sackboy-spike-ratchet-and-clank/comment-page-2/#comments
4 ≈ One