A series of blue-emitting Ca2 - xEuxPO4Cl phosphors were synthesized by a solid state method in a reducing atmosphere. The factors those affect the structure and the photoluminescence (PL) intensities of phosphors, including the dosage of chlorine source CaCl2, reaction time and annealing temperature, have been investigated in detail. X-ray diffraction (XRD) and photoluminescence measurements were performed to testify the crystal structure and luminescent properties. The optimal Eu2+ concentration was determined, and the mechanism of the concentration quenching was predominated by dipole-dipole interaction. The present phosphor exhibits a strong absorption in the near-UV region, emits an intense blue emission centered at 451 nm and presents excellent thermal stability, suggesting that the phosphor is competitive as a promising blue-emitting phosphor for near ultraviolet (n-UV) light-emitting diodes (LEDs).