Ca-5[(P,V)O-4)](3)F:Eu3+ red-emitting phosphors were synthesized by a solid-state method. The effect of [PO4](3)/[VO4](3-) substitution on the structures and luminescence properties have been discussed. Apatite-type Ca-5[(P,V)O-4)](3)F:Eu3+ phosphors are obtained, and the lattice parameters a, c values and cell volume V increase with the increasing content of [VO4](3-) substitution for [PO4](3-). The optimum Eu3+ doping concentration in a selected system has been studied. The variations of the emission and excitation spectra of Ca-5[(P,V)O-4)](3)F:Eu3+ phosphors depending on the varied [PO4](3-)//[VO4](3-) substitution amounts have been discussed. The mechanism on the broadening of the excitation band with increasing [VO4](3-) contents has been analyzed. (C) 2015 Elsevier B.V. All rights reserved.