In order to solve the drawbacks of color reabsorption and ratio tuning among phosphor mixtures, a series of Ba_4-xCe₃Na₃(PO₄)₆F₂:xEu²⁺ color-tunable luminescent materials are 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). Combined with the fluorescence decay curve, it proves that there is an obvious energy transfer from Ce³⁺ to Eu²⁺.