Ba x Zn 1−x MoO 4 :Eu 3+ (0.1 ≤ x ≤ 0.7) red phosphors were synthesized at the temperature of 800 °C by solid-state reaction method in air atmosphere. The structures of the phosphors were characterized by X-ray diffraction and Raman spectra. Photoluminescence (PL) spectra were also used to investigate the photoluminescent properties of the phosphors. The experimental results indicated that the introduction of Ba 2+ enhanced the emission at 615 nm. The different Ba 2+ /Zn 2+ ratios of the molybdate phosphors caused the corresponding changes of photoluminescent properties. The variation of photoluminescent intensity with Ba 2+ concentration as well as with different excitation wavelengths was discussed systematically. Ba x Zn 1−x MoO 4 :Eu 3+ phosphors with the optimal compositions of x = 0.5 exhibited satisfactory and excellent PL and the intensity of the emission at 615 nm was about three times stronger than that of ZnMoO 4 :Eu 3+ , which could be applied as red-emitting phosphors excited by ultra-violet and blue chips in white light-emitting diodes.