In this paper, a series of Ca4-xY5.95 (SiO4)6F2: 0.05Ce3+, xMn2+ phosphors with an apatite structure were synthesized by the high-temperature solid phase method; their photoluminescence properties and energy transfer behavior were investigated. The obtained phosphors exhibit a broad excitation band ranging from 200 to 375 nm and also broad emission bands with two peaks centered at 408 and 602 nm monitored at 325 nm excitation, which originate from 5d→4f transition of Ce3+ and 4T1 (4G)→6A1 (6S) transition of Mn2+, respectively. The energy transfer from Ce3+ to Mn2+ was confirmed by spectral overlap phenomenon and decay curve measurements. Based on the analysis of the energy level structure of Ce3+and Mn2+, the existence of the energy transfer from Ce3+→Mn2+ was further confirmed.