The game welcomes both Jak and Daxter and inFAMOUS protagonist Cole MacGrath.
The announcement was accompanied by a new trailer, which showcases the character's abilities and special moves.
Jak's weapons include the Blaster, Needle Lazer, Gyro Burster and Mass Inverter. Players will also have the ability to unleash the powers of both Dark and Light Jak.
Cole, meanwhile, retains his electrokinesis and cryokinesis powers, making him a good long-range fighter.
Users who pre-order the title will also receive a bonus of an exclusive additional costume for every character in the game.
Additional characters include Fat Princess, Sly Cooper, Colonel Radec from Killzone, Parappa the Rapper, Kratos from God of War, Nathan Drake from Uncharted, Sweet Tooth from Twisted Metal and the Big Daddy from Bioshock.
Street Fighter advisor Seth Killian recently left Capcom in order to join Sony Santa Monica as the lead game designer for PlayStation All-Stars Battle Royale.
The game will offer single-player and multiplayer modes, including support for up to four players locally, cross-platform play between PS3 and Vita and a number of online tournament options.
The mascot fighting game will arrive on PlayStation 3 and Vita on October 23 in North America and on October 24 across Europe.
Screenshots gallery - PlayStation All-Stars Battle Royale: