For the first time, a series of Ce 3+ /Dy 3+ single-doped and co-doped orthophosphate CaHf 4 (PO 4 ) 6 (CHPO) samples were produced by solid-state reaction technique in a carbon reduction environment. The morphology, crystal structure, photoluminescence characteristics, and energy transfer between ions were investigated. The crystal structure was confirmed to be a diamond-shaped NASICON-type structure of the R3c space group. By investigating the photoluminescence emission and excitation spectra of the samples, we have verified the existence of the energy transfer from Ce 3+ to Dy 3+ . The energy transfer efficiency was calculated and the mechanism was determined as dipole-quadrupole interaction. Temperature-dependent photoluminescence experiments confirmed the good thermal stability of the samples. By adjusting the concentration ratio of Ce 3+ and Dy 3+ under UV illumination, tunable emission from blue-purple to yellow-white could well be achieved. The CIE coordinate of the 4% Ce 3+ and 4% Dy 3+ co-doped sample is (0.291,0.308), i.e., blue-white color. It is suggesting that CHPO: Ce 3+ , Dy 3+ could be interesting candidate materials in the applications of ultraviolet-excited WLEDs.