Hafnium-based materials are attractive for a scintillator owing to their high density and effective atomic number. In this study, single crystals of Ce-doped calcium hafnate perovskite (Ce:CaHfO3) were synthesized from a Ca-rich composition, and photoluminescence (PL) and scintillation properties were investigated. The X-ray diffraction patterns revealed that the synthesized single crystals were a single phase of CaHfO3. The Ce:CaHfO3 exhibited blue luminescence at 430 nm and fast decay due to the 5d-4f transition of Ce3+ in both PL and scintillation. From the measurement of pulse height spectra under Cs-137 irradiation, the highest light yield of 7800 photons/MeV was observed in the 3% Ce:CaHfO3.