Single-phase La6Sr4(SiO4)6F2: Ce3+, Tb3+ samples with apatite-like structure have been synthesized via solid-state reaction method. The phase structure, luminescence properties, lifetime, the PL thermal stability, as well as the fluorescence decay curves of the samples were investigated to characterize the resulting samples. Effective energy transfer occurs from Ce3+ to Tb3+ in La6Sr4(SiO4)6F2, which shows more intense Blue-Green light under UV light excitation. In addition, a possible mechanism of the energy-transfer from Ce3+ to Tb3+ ion is also proposed. The critical distance RC of Ce3+ to Tb3+ ions in La6Sr4(SiO4)6F2 host was calculated to be 11.878Å. All the results indicate that La6Sr4(SiO4)6F2:Ce3+, Tb3+ phosphors have potential applications to be used as near UV-convertible phosphors for white light-emitting diodes.