A series of blue-to-white emitting phosphors NaAlSiO4: Ce3+, Mn2+ were synthesized via a high-temperature solid-state method. The obtained phosphors exhibited a broad excitation band from 250 to 400nm peaking at 350nm, matching well with the available UV chips. Under the excitation of 350nm, a broad green–blue emission band peaking at 430nm and an orange–red emission band at 590nm were observed due to the f–d transition of Ce3+ and the 4T1–6A1 transition of Mn2+, respectively. Moreover, energy transfer process from Ce3+ to Mn2+ was verified with the mechanism to be dipole-quadrupole interaction. By varying the doping concentration of Mn2+, tunable colors from blue to white were obtained in the phosphors. The results indicate that this phosphor has potential applications as a single-phased aluminosilicate phosphor for ultraviolet white light-emitting diodes (UVWLEDs).