Eu2+ and Eu2+/Mn2+-activated Na5Ca2Al(PO4)(4) phosphors have been synthesized by the combustion method. X-ray powder diffraction profiles, luminescence spectra, chromaticity variation, and energy transfer of Na5Ca2Al(PO4)(4):Eu2+, Mn2+ were investigated as a function of the Eu2+ and Mn2+ concentrations in Na5Ca2Al(PO4)(4). The Na5Ca2Al(PO4)(4):Eu2+,Mn2+ phosphors can be effectively excited at wavelength ranging from 300 to 430nm, which matches well with that for near-ultraviolet (UV) light-emitting diode (LED) chips. Under excitation at 354nm, Na5Ca2Al(PO4)(4):Eu2+,Mn2+ not only exhibits blue-green emission band attributed to 4f(6)5d(1)4f(7) of Eu2+ but also gives an orange emission band attributed to (4)T(1)(6)A(1) of Mn2+. The emission color of the phosphor can be systematically tuned from blue-green through white and eventually to orange by adjusting the relative content of Eu2+ and Mn2+ through the principle of energy transfer. The results indicated that Na5Ca2Al(PO4)(4):Eu2+, Mn2+ may serve as a potential color-tunable phosphor for near UV white-light LED.