CaHfO3 was investigated as a promising candidate for a scintillator because of high density and large effective atomic number. Tb-doped CaHfO3 single crystals with various Tb concentrations were synthesized by the floating zone method, and the photoluminescence (PL) and scintillation properties were investigated. All the samples showed the highest PL emission intensity at 550 nm, and the origin of this emission was identified as 4f-4f transitions of Tb3+ by the obtained PL decay time constants. The X-ray-induced scintillation spectra showed several emission peaks in the range of 350–650 nm, which were attributed to the 4f-4f transitions of Tb3+. Based on the results of the pulse height spectra, the light yield of the 1.0% Tb-doped sample was calculated to be 12,000 photons/MeV, respectively.