Ce 3+ /Mn 2+ ions-doped oxyapatite calcium fluorapatite [Ca 5 (PO 4 ) 3 F, FAP] has been successfully synthesized by a facile one-step hydrothermal method. The luminescent properties of Ce 3+ - and Ce 3+ /Mn 2+ - activated FAP phosphors were investigated using the photoluminescence (PL) and photoluminescence excitation (PLE) spectra. The emission of Ce 3+ was fitted by two Gaussian functions with dashed lines in wavenumber to confirm the Ce 3+ ion simultaneously to occupy the 4f and 6h sites in Ca 5 (PO 4 ) 3 F host, which was consistent with the calculated results of crystal field based on chemical bond theory. In addition, the existence of Ce 3+ (sensitizer) can dramatically enhance the green emission of Mn 2+ (activator) in Ce 3+ /Mn 2+ ions co-doped samples due to an efficient energy transfer from Ce 3+ to Mn 2+ . All of these results could help us understand the site assignments and optical properties of the rare earth ions doped in hexagonal Ca 5 (PO 4 ) 3 F.