The luminescence of LaY3+ and ScY3+ and ScAl3+ centers created by lanthanum and scandium ions at Y3+ and Al3+ cation sites of YAlO3 perovskite lattice was investigated. The features of emission of excitons localized at the mentioned centers in YAlO3:La and YAlO3:Sc single-crystalline films were analyzed by means of time-resolved emission spectroscopy and luminescence decay kinetics measurements under excitation by synchrotron radiation at 9 and 300 K.