The 7 mm undoped Cs2HfCl6 and Cs2HfCl6∶0.2%Tl(mole fraction) single crystals were grown by the Vertical Bridgman method. The phase, impurities concentrations, luminescence and scintillation properties of crystal samples were studied. Both crystalsbelong to the cubic crystal structure and the space group of Fm3m. When excited by ultraviolet light and X-ray, both crystals exhibit an emission peak at 380 nm originated from self-trapped excitons emission, and Cs2HfCl6∶0.2%Tl crystal exhibits an extra Tl+ sp-s2 transition induced emission at 505 nm. Cs2HfCl6 and Cs2HfCl6∶0.2%Tl possess high light yields of 37 000 photons/MeV and 36 500 photons/MeV respectively and both have excellent energy resolutions of 3.5% at 662 keV under excitation of 137Cs source. The scintillation decay time of undoped Cs2HfCl6 is comprised of 0.37 μs (4.2%), 4.27 μs (78.9%) and 12.52 μs (16.9%). The scintillation decay time of Cs2HfCl6∶0.2%Tl is comprised of 0.33 μs (3.5%), 4.09 μs (81.9%) and 10.42 μs (14.5%).