ZnO/Bi4V2O[Formula: see text] nanocomposites were prepared via a facile hydrothermal method by loading different amounts of ZnO onto the surface of Bi4V2O[Formula: see text]. The resulting ZnO/Bi4V2O[Formula: see text] composites showed excellent photocatalytic activity than that of pure ZnO under visible light irradiation. When the ratio of ZnO to Bi4V2O[Formula: see text] was 1:1 (ZB2), the photocatalytic activity was best, which could degrade RhB almost completely within 30[Formula: see text]min. The enhanced photocatalytic activity of ZnO/Bi4V2O[Formula: see text] composites could be mainly ascribed to the efficient charge separation and the increased specific surface area. Based on the experimental and bandgap calculations, a possible photocatalytic mechanism was proposed.