A series of red emitting Ca8La2(PO4)6O2:xEu3+ (0≤x≤0.4) phosphors were synthesized by the conventional solid state reaction, and their photoluminescence properties were investigated in this work. Upon excitation of blue light, the Ca8La2(PO4)6O2:xEu3+ phosphors exhibit strong red emission at 616nm, which corresponds to the dominant transition of Eu3+ ions in Ca8La2(PO4)6O2 host, originating from the electric dipole transition 5D0–7F2. Moreover, Ca8La2(PO4)6O2:0.3Eu3+ phosphor shows more intense photoluminescence than that of other phosphors, where the concentration of Eu3+ ion is not equal to 0.3. The CIE chromaticity coordinate (0.657, 0.343) of Ca8La2(PO4)6O2:0.3Eu3+ phosphor is close to National Television Standard Committee standard value (0.670, 0.330) of red phosphors, which indicates Ca8La2(PO4)6O2:0.3Eu3+ is potential to apply in white light-emitting diodes as an excellent red emitting phosphor.