Large-size scintillators with high efficiency and ultrafast radiation fluorescence have shown more potential in the applications to ionizing radiation detection of medical diagnosis, nuclear control and high-energy physics. Currently, although traditional scintillators have made tremendous progress in scintillation efficiency, there are still challenges left in fluorescence lifetime. Faced with that problem, we adopted 2-inch ZnO as the substrate and doped gallium as activator to realize an ultrafast fluorescence excited by α-ray, of which the decay time is only 600 ps that is the shortest scintillation decay time reported so far. The results show that the shallow donor related with gallium not only effectively suppresses band-edge self-absorption, but makes ultrafast radiation possible, which gets gallium-doped ZnO as a potential scintillator for high-quality ultrafast dynamic imaging proved.