A novel octahedron-like hierarchical structure of Bi2WO 6 has been fabricated by a facile hydrothermal method in high quantity. XRD, SEM, TEM, and HRTEM were used to characterize the product. The results indicated that this kind of Bi2WO6 crystals had an average size of ~4 μm, constructed by quasi-square single-crystal nanosheets assembled in a special fashion. The formation of octahedron-like hierarchical structure of Bi2WO6 depended crucially on the pH value of the precursor suspensions. The photocatalytic activity of the hierarchical Bi2WO6 structures toward RhB degradation under visible...