Ce3 + and Mn2 + co-doped Ca4Si2O7F2 phosphors have been synthesized by high temperature solid state reaction and their luminescence properties are investigated. The effect of Ce3 + concentration on the emission intensity of Ca4Si2O7F2: Ce3 + is studied, and the emission intensity reaches a maximum at 4% Ce3 +. Energy transfer from Ce3 + to Mn2 + is observed. The emission spectra of the phosphors show a blue broad band at 460 nm of Ce3 + and a yellow band at 580 nm of Mn2 +, originate from the allowed 5d → 4f transition of the Ce3 + ion and the 4T1g(4G) → 6A1g(6S) transition of the Mn2 + ion, respectively. Results indicate that the varied emitted color from blue to yellow can be achieved by tuning the relative ratio of the Ce3 + to Mn2 + ions based on the principle of energy transfer. We have demonstrated that Ca4Si2O7F2: Ce3 +, Mn2 + phosphors can be a promising candidate for a color-tunable phosphor applied in a near-UV White light emitting diodes.