The ones coming to both PS4 and Vita include:

Assault Android Cactus (Witch Beam)
FEZ (Polytron Corporation)
Final Horizon (Eiconic Games)
Hotline Miami 2: Wrong Number (Dennaton Games and Devolver Digital)
Rogue Legacy (Cellar Door Games)
Samurai Gunn (Teknopants)
Switch Galaxy Ultra (Atomicom)
The Binding of Isaac: Rebirth (Nicalis)
Velocity 2X (FuturLab)
Volume (Mike Bithell)
Wasteland Kings (Vlambeer

PS4-exclusive:

N++ (Metanet)
Guns of Icarus Online (Muse Games)
Starbound (Chucklefish)