Ba[Formula: see text](PO4)2:0.04Eu[Formula: see text] (S1) and Ba[Formula: see text]Na[Formula: see text](PO4)2:0.04Eu[Formula: see text] (S2) were prepared by solid state reaction. The phases and luminescent properties of the obtained phosphors were characterized. The results demonstrate that the phosphors particles emit an intensive red light under excitation at 395 nm. Both phosphors can be efficiently excited by ultraviolet and blue light, and the emission spectra mainly consist of two emission peaks at 591 nm and 611 nm. The crystallographic sites of Eu[Formula: see text] ions in Ba3(PO4)2 host were discussed on the base of emission spectra and its host crystal structure. By introducing the charge compensator Na[Formula: see text] into the S1 phosphor, its emission intensity was enhanced, indicating that S2 could serve as a promising red-emitting phosphor for UV LED applications.