A series of beta-Na2Ca4(PO4)(2)(SiO4) (beta-NCPS):A (A = Eu2+, Dy3+, Ce3+/Tb3+) phosphors were prepared via a high-temperature solid-state reaction route. The X-ray diffraction, Fourier transform infrared, photoluminescence (PL), cathodoluminescence (CL) properties, fluorescent lifetimes, and absolute quantum yield were exploited to characterize the samples. Under UV radiation, the beta-NCPS:Eu2+ phosphors present bright green emissions, and the beta-NCPS:Ce3+ phosphors show strong blue emissions, which are attributed to their 4f(6)5d(1) -> 4f(7) and Sd-4f allowed transitions, respectively. The beta-NCPS:Ce3+, Tb3+ phosphors display intense tunable color from blue to green and high absolute quantum yields (81% for beta-NCPS:0.12Ce(3+) and 83% for beta-NCPS:0.12Ce(3+), 0.08Tb(3+)) when excited at 365 nm. Simultaneously, the energy transfer from Ce3+ to Tb3+ ions is deduced from the spectral overlap between Ce3+ emission and Tb3+ excitation spectra and demonstrated by the change of emission spectra and decay lifetimes. Moreover, the energy-transfer mechanism from Ce3+ to Tb3+ ions is confirmed to be exchange interaction according to the discussion of expression from Dexter and Reisfeld. Under a low-voltage electron-beam excitation, the beta-NCPS:A (A = Eu2+, Dy3+, Ce3+/Tb3+) phosphors exhibit their characteristic emissions, and the emission profiles of beta-NCPS:Ce3+,Tb3+ phosphors are obviously different from those of the PL spectra; this difference might be ascribed to their different luminescence mechanisms. These results in PL and CL properties suggest that beta-NCPS:A (A = Eu2+, Dy3+, Ce3+/Tb3+) phosphors are potential candidates for solid-state lighting and field-emission displays.