Ce3+/Mn2+ ions-doped oxyapatite calcium fluorapatite [Ca-5(PO4)(3)F, FAP] has been successfully synthesized by a facile one-step hydrothermal method. The luminescent properties of Ce3+- and Ce3+/Mn2+- activated FAP phosphors were investigated using the photoluminescence (PL) and photoluminescence excitation (PLE) spectra. The emission of Ce3+ was fitted by two Gaussian functions with dashed lines in wavenumber to confirm the Ce3+ ion simultaneously to occupy the 4f and 6h sites in Ca-5(PO4)(3)F host, which was consistent with the calculated results of crystal field based on chemical bond theory. In addition, the existence of Ce3+ (sensitizer) can dramatically enhance the green emission of Mn2+ (activator) in Ce3+/Mn2+ ions co-doped samples due to an efficient energy transfer from Ce3+ to Mn2+. All of these results could help us understand the site assignments and optical properties of the rare earth ions doped in hexagonal Ca-5(PO4)(3)F. (C) 2014 Elsevier Ltd. All rights reserved.