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Bi₂WO₆ hollow structures consisting of nanoparticles with diameters of 10–20nm were synthesized by a facile and reproducible solvothermal method in the presence of ethylene glycol. The obtained Bi₂WO₆ hollow structures exhibit higher photocatalytic activity towards the degradation of Rhodamine B (RhB) under visible-light irradiation, up to 99% within 40min, which was much higher than P25-TiO₂. The enhanced photocatalytic performance could be attributed to their tiny building blocks as well as high BET surface areas (65.04m²g⁻¹). The obtained Bi₂WO₆ hollow structures are chemically stable, and the efficiency remained almost the same after recycled five times, suggesting that Bi₂WO₆ hollow structures are promising visible-light photocatalyst for practical applications.