A series of chalcogenide apatites phosphors Ca-10(PO4)(6)Y:Ce (Y = S, Se) were prepared using high-temperature solid-state reaction technique. Their luminescent spectra together with decay time spectra at room temperature were investigated and discussed. The results revealed that Ca(I) sites are preferentially occupied at low-doping concentration, and Ca(II) sites are dominant with the increasing of concentration for Ce3+ in Ca-10(PO4)(6)S. In contrast, Ce3+ ions mainly occupied the Ca(II) sites in Ca-10(PO4)(6)Se even at lower doping concentration. For the iso-structure apatites M-10(PO4)(6)Y (M = Ca, Y = 2F, S), the different anions Y surrounding M(II) have little influence on the M(I)-O character. (C) 2008 Elsevier B.V. All rights reserved.