A novel Ba2MgMoO6:Eu3+ orange-red phosphor was synthesized by the Pechini method and characterized by x-ray diffraction. Photoluminescence properties of BaMgMoO6:Eu3+ phosphors have been represented in the excitation and emission spectra. The charge transfer (CT) band of Ba2MgMoO6 host is situated at near-ultraviolet (UV) region, whose central wave length and bandwidth are 394 and 80 nm, respectively. And it matches well the emission wave length from near-UV light emitting diodes (LEDs). The most intensive emission of 5D0 → 7F1 (598 nm) of Eu3+ in Ba2MgMoO6:Eu3+ is much narrow with a full width at half-maximum less than 2 nm under excitation with either CT band or 394 nm. And a low concentration quenching occurs in Ba2MgMoO6:Eu3+, and the optimal doping concentration is about 0.05. The mechanism of charge and energy transfer from Ba2MgMoO6 host to Eu3+ is proposed and analyzed on the basis of its crystal structure. In a word, Ba2MgMoO6:Eu3+ may be a promising orange-red component for near UV white LEDs.