The ultraviolet photoluminescence of ZnO/ZnGa2O4 composite layer grown by the thermal oxidation of ZnS with gallium was investigated by the time-resolved photoluminescence as a function of measuring temperature and excitation power. With increase of excitation power, the D0X emission is easily saturated than the DAP emission from ZnO/ZnGa2O4 composite layer, and which is dramatically enhanced as compared with that from pure ZnO layer grown without gallium. The radiative recombination process with ultra-long lifetime controlled the carrier recombination of ZnO/ZnGa2O4 composite layer.