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Found this out when I was playing with my buddy, you can sign in your second controller as another account off your ps3.
Can someone confirm this? I thought it was on xbox only where you could play split screen using two different online accounts. I may be wrong though because Borderlands 2 can have 2 users on split screen, but I do believe that it's because BL 2 uses save files and doesn't save progress on a server. Can someone please confirm if you can play as two different psn's ?