A series of novel single-phase Ca9NaZn(PO4)7∶Ce3+, Mn2+are synthesized by a high temperature solidstate reaction method, and the luminescence properties and energy transfer process are investigated systematically. When excited by 303 nm, the Ce3+ and Mn2+ co-doped phosphor exhibited two emission peaks centered at 374 nm and 63 nm, which are ascribed to 5d → 4f and 4T1 (4G) → 6A1 (6S) transition of Ce3+ and Mn2+, respectively. The results show that the existence of efficient energy transfer between Ce3+ and Mn2+ can dramatically enhance the emission intensity of Mn2+, the critical distance is calculated to be 1.385, and this process has been proved to be a resonant type via a dipole-quadrupole interaction. Ultimately, the corresponding CIE coordinates intuitively show the tunable colors from the violet-blue to red area by controlling the relative composition of Ce3+ and Mn2+ content.