A series of Ba4Gd3Na3(PO4)(6)F-2:Eu2+ phosphors with a broad emitting band have been synthesized by a traditional solid state reaction. The crystal structural and photoluminescence properties of Ba4Gd3Na3(PO4)(6)F-2:Eu2+ are investigated. The different crystallographic sites of Eu2+ in Ba4Gd3Na3(PO4)(6)F-2:Eu2+ phosphors have been verified by means of their photoluminescence (PL) properties and decay times. Energy transfer between Eu2+ ions, analyzed by excitation, emission, and PL decay behavior, has been indicated to be a dipole-dipole mechanism. Moreover, the luminescence quantum yield as well as the thermal stability of the Ba4Gd3Na3(PO4)(6)F-2:Eu2+ phosphor have been investigated systematically. The as-prepared Ba4Gd3Na3(PO4)(6)F-2:Eu2+ phosphor can act as a promising candidate for n-UV convertible white LEDs.