A series of Ce³⁺, Eu²⁺and Ce³⁺-Eu²⁺doped Ca₉Al(PO₄)₇phosphors are synthesized by a high temperature solid-state method. Under 291 nm excitation, Ca₉Al(PO₄)₇:Ce³⁺has one emission band at 356 nm, which is attributed to 4f05d1→4f1 transition of Ce³⁺. Under 305 nm excitation, Ca₉Al(PO₄)₇:Eu²⁺presents one emission band at 445 nm, which is assigned to 4f 65d1→4f 7 transition of Eu²⁺. Energy transfer from Ce³⁺to Eu²⁺in Ca₉Al(PO₄)₇is validated and proved to be a resonant type via a quadrupole-quadrupole interaction. Critical distance (Rc) of Ce³⁺to Eu²⁺in Ca₉Al(PO₄)₇is calculated to be 1.264 nm. Moreover, the emission intensity of Ca₉Al(PO₄)₇:Ce³⁺, Eu²⁺can be tuned by properly adjusting the relative doping composition of Ce³⁺/Eu²⁺.