Novel orange-red emitting phosphors, Ba2Zn1-xWO6:xSm3+ (x = 0.03, 0.04, 0.05, 0.06 and 0.07) (BZW:Sm3+), were prepared using a high-temperature solid-state reaction method. Their crystal structure and photoluminescence properties were characterized and the mechanism of energy transfers between Ba2ZnWO6 and Sm3+ elucidated in detail. It was found that the phosphors had a cubic structure with space group Fm3¯m. They can be excited by near-ultraviolet light, and the characteristic emissions of Sm3+ ions are observed at 564 nm, 598 nm and 645 nm, corresponding to 4G5/2 → 6H5/2, 4G5/2 → 6H7/2 and 4G5/2 → 6H9/2 transitions, respectively. The 4G5/2 → 6H9/2 transitions shows the greatest intensity, which indicates that Sm3+ ions occupy the noncentrosymmetric sites. The optimal doping concentration of Sm3+ ions in Ba2ZnWO6 is about 5 mol% and the phenomenon of concentration quenching occurs when the content of Sm3+ ions exceeds 5 mol%. All results show that the Ba2ZnWO6:Sm3+ phosphor holds great promise for use in high-quality white light-emitting diodes.