In order to solve the drawbacks of color reabsorption and ratio tuning among phosphor mixtures, a series of Ba4-xCe3Na3(PO4)6F2:xEu2+ color-tunable luminescent materials were synthesized successfully by high-temperature solid-state method. Under the 297 nm excitation, the emission spectra of the phosphor consist of two emission bands, the yellow light with the peak at 570 nm is assigned to the 4f65d1→4f7 transition of Eu2+, and the luminescence centers red-shifted from 380 nm to 470 nm is assigned to the transition from 4f65d1 to 4f7 of Ce3+. With increasing the Eu2+ doping concentration, the emission region of phosphor gradually moves from the blue region to the yellow region, and the chromaticity coordinates (CIE) also turn from (0.056, 0.069) to (0.303, 0.347), which indicates that there is an obvious energy transfer from Ce3+ to Eu2+.