{010}-Oriented flower-like Bi2WO6 with high adsorptivity and photoactivity was prepared via a hydrothermal method without any additives under neutral environment. The anisotropic flower-like Bi2WO6 shows greatly enhanced adsorptivity and photoactivity compared with isotropic particle Bi2WO6 as well as most of other forms of Bi2WO6. The superior adsorptivity shows potential in suitability for majority of dyes. Detailed study on microstructure and morphology indicates that mesoporous structure and large surface area mainly contribute to the superior properties. Especially, {010} crystal planes of flower-like Bi2WO6 terminated with [Bi2O2](2+) layers provide more adsorption sites for dyes than other facets. In combination with first-principles calculations, it is initially revealed that {010}-oriented facets preference benefits hole distribution at surface and provides the most reactive sites, thus enhances the photoactivity of the flower-like Bi2WO6. Moreover, the anisotropic flower-like Bi2WO6 shows excellent recyclability and cycling stability with great potential in environmental applications. (C) 2014 Elsevier B.V. All rights reserved.