3D Dot Game Heroes, the Atelier series (the first one is getting a remake, wait for that),  Catherine (also on 360 but this is the best version), Demon's Souls, DMC HD Collection, Disgaea 3 and 4, Dragon's Crown,
 Dragon's Dogma: Dark Arisen, Eternal Sonata, the later Neptunia games (if that's your thing, they're pretty good, first is getting a remake on the vita, first is shit otherwise), the Ico and SotC HD collection,
 Katamari Forever (it's not the best katamari game but it's a katamari game), LittleBigPlanet 2 (can't really vouch for this but i've heard good things from good people), Metal Gear Rising: Revengance, Ni No Kuni,
 Ninja Gaiden Sigma 1 + 2 (also has a vita port, in fact, a lot of stuff I listed does), No More Heroes: Heroes' Paradise, Persona 4 Arena, Ratchet and Clank Collection (never played the games, just heard good things),
 Rayman Legends (basically on every platform, Wii U/Vita version is the best, and PC coming at second), Red Dead Redemption: GotY (one of my personal favorites), Resonance of Fate,
 Rune Factory: Tides of Destiny (can't exactly vouch for it), Siren: Blood Curse (J-horror, same guy as the first four Silent Hill games), The Sly Collection (same thing as R&C: C), Sonic Generations (on all platforms, PC is the best),
 Soul Calibur V, Tales of Graces F and Tales of Xillia (both are fantastic games, must plays. Tales of Symphonia series remake coming soon), Uncharted 2 (GotY), Valkyria Chronicles,
 Yakuza 3, 4 (I think the first two can be emulated, not required but strongly recommended. Yakuza 5 localization probably coming never.), Hatsune Miku: Project Diva F (very damn good, pretty much required.), Final Fantasy 10+-2) HD,
 Okami HD, Beyond Good and Evil HD, Mega Man 9 and 10 (also on Wii, it's a better port, not because of sub-HD visuals but because the best controls), Grand Theft Auto V (Probably going to be really fucking good),
 Dark Souls (PC version is the best, obviously.), Dark Souls II (It's upcoming, however the PC version is again, the best.), Lighting Returns: Final Fantasy XIII (it COULD be good, XIII was horrible, XIII-2 was okay,
 however this is actually looking good.) Keep in mind, these are my personal opinions, there are definitely more games on the console that you could enjoy, but the games I listed are probably all pretty damn enjoyable.