Natural scapolite including the S-2 impurity is a typical silicate luminescent mineral. According to the formation conditions and chemical composition of natural scapolite, we synthesized Na4Ca4Al6Si9O24(scapolite) by the high temperature solid-phase reaction, and prepared the synthetic scapolite phosphors activated with Ce3+ and Tb3+. The photoluminescence (PL) properties of the obtained phosphors were studied. The results indicated that the PL intensity of green (545 nm) emission corresponding to the 5D4 →7F5 transition within Tb3+in the Ce3+, Tb3+-codoped samples was much higher than that of the Tb3+-doped samples. The PL properties of the samples activated with various Ce3+ concentrations were measured, and their fluorescence lifetime and energy transfer mechanism were analyzed. We proved that there was energy transfer from Ce3+ to Tb3+, and the energy transfer efficiency was at its maximum when the Ce3+ to Tb3+ mass ratio was 0.02∶0.03. Upon measurement by chromaticity coordinates, we found that the luminescence of the samples could be adjusted in the green area with varying Ce3+ concentrations. We thus deem that scapolite phosphors Na4Ca4Al6Si9O24∶Ce3+, Tb3+ are promising to become the new white LED phosphors.