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The ZnWO4 photocatalysts doped with different molar ratios of molybdenum ions have been successfully prepared by a facile and effective hydrothermal method. The photocatalytic activities of the as-prepared products were evaluated by the degradation of rhodamine B (RhB) in aqueous solution. The result showed that with the doping of molybdenum ions, the photocatalytic activity of the Mo-doped ZnWO4 photocatalysts were greatly improved. In addition, the best photoactivity was acquired when the Mo-doping molar ratio is 0.05. The doping effects on the properties of ZnWO4 nanoparticles such as particle size, specific surface area, band gap and the photocatalytic performance were systematically discussed.