Eu2+ and Mn2+ coactivated -Ca-3(PO4)(2) (TCP) phosphors have been prepared by high-temperature solid-state reaction. The site occupation and photoluminescence properties of Eu2+ and Mn2+ have been identified and discussed in detail. The energy transfer from Eu2+ to Mn2+ in TCP: Eu2+, Mn2+ phosphors has been validated and demonstrated to be a resonant type via a dipole-quadrupole mechanism, and the critical distance (R-C) calculated by concentration quenching method is 21.76 angstrom. A color-tunable emission from violet-blue to red in TCP: Eu2+, Mn2+ phosphors can be realized via the energy transfer from Eu2+ to Mn2+ ions.