A series of NaCa13/Mg-18(5)/18PO4(NCMPO):A (A = Eu2+/Tb3+/Mn2+, Dy3+) phosphors have been prepared by the high-temperature solid-state reaction method. The X-ray diffraction (XRD) and Rietveld refinement, X-ray photoelectron spectroscopy (XPS), photoluminescence (PL), cathodoluminescence (CL), decay lifetimes, and PL quantum yields (QYs) were utilized to characterize the phosphors. The pure crystalline phase of as-prepared samples has been demonstrated via XRD measurement and Rietveld refinements. XPS reveals that the Eu2+/Tb3+/Mn2+ can be efficiently doped into the crystal lattice. NCMPO:Eu2+/Tb3+/Mn2+ phosphors can be effectively excited under UV radiation, which show tunable color from purple-blue to red including white emission based on energy transfer from Eu2+ to Tb3+/Mn2+ ions. Under low-voltage electron beam bombardment, the NCMPO:A (A = Eu2+/Tb3+/Mn2+, Dy3+) display their, respectively, characteristic emissions with different colors, and the CL spectrum of NCMPO:0.04Tb(3+) has the comparable intensity to the ZnO:Zn commercial product. In addition, the calculated CIE coordinate of NCMPO:0.04Tb(3+) (0.252, 0.432) is more saturated than it (0.195, 0.417). These results reveal that NCMPO:A (A = Eu2+/Tb3+/Mn2+, Dy3+) may be potential candidate phosphors for WLEDs and FEDs.