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Dual-functional ZnWO4:Dy3+, Bi3+ were synthesized via high-temperature solid-state reaction method. The as-prepared samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), photoluminescence spectra and photocatalytic properties. The ZnWO4:Dy3+, Bi3+ phosphor shows photoluminescence with a broad band and the feature Dy3+ emission, and a high photocatalytic activity in degradation of Rhodamine B (RhB) under simulated UV irradiation. The result shows that doping Bi3+ in ZnWO4:Dy3+ can enhance light harvest capability to generate more electron-hole pairs, and acted as a trap center by decreasing the recombination of photogenerated electrons and holes. All of the results obtained by the work suggest that ZnWO4:Dy3+, Bi3+ phosphors are promising materials for the photocatalytic decomposition of pollutants. [ABSTRACT FROM AUTHOR]