The platform holder confirmed at its E3 2012 conference that the likes of Tomb Raider and Final Fantasy will be coming to the handheld.
Games from Sony's back catalogue were already available for the PlayStation 3 and PlayStation Portable via the firm's online store, but they were incompatible with the Vita upon its launch.
Sony also announced the addition of new entertainment apps for the device, including video services Hulu Plus and Crackle.
Other highlights from Sony's E3 conference include the announcement that HTC has become an official PlayStation partner, and confirmation of Assassin's Creed 3 and Call of Duty Black Ops iterations for the handheld.
Sony also announced a March 2013 release for God of War Ascension and unveiled a new game from Quantic Dream called Beyond.
> Digital Spy's E3 Gaming Expo 2012 complete coverage