A series of hierarchical flower-like hollow structure Ag2WO4/WO3 photocatalysts was synthesized and characterized by XRD, SEM, Raman spectroscopy, XPS, photoluminescence (PL) spectra, and BET. The obtained results indicated the growth of finely distribution of Ag2WO4 on the surface of the WO3 hollow sphere. UV-vis diffuse reflectance spectroscopy (DRS) was used to investigate the absorption range and band gap of photocatalysts. The photocatalytic activities of the photocatalysts were evaluated by the decolorization of Rhodamine B (RhB) under visible-light irradiation. The results showed that the highest activity could be reached up to 94%. It was also found that the heterojunction structure photocatalyst exhibited excellent stability. The kinetic reaction rate of heterojunction structure photocatalyst was nearly 17.0 and 7.5 times higher than those of pure WO3 and Ag2WO4. A possible photocatalytic mechanism for decolorization of Rhodamine B was proposed. (C) 2017 Elsevier B.V. All rights reserved.