In this work, Bi2WO6 with complex morphologies, namely, flower-like, pancake-like, and tubular shapes have been controllably synthesized by a facile solvothermal process. The as-obtained samples are systematically investigated using X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and high resolution transmission electron microscopy (HRTEM). The effects of solvents on the morphologies of Bi2WO6 nanostructures are systematically investigated. According to the time-dependent experiments, a two-step growth mode basing on Ostwald ripening process and self-assembly has been proposed for the formation of the flower-like and pancake-like Bi2WO6 nanostructures. The photocatalytic properties of Bi2WO6 nanostructures are strongly dependent on their shapes, sizes, and structures for the degradation of rhodamine B (RhB) under visible-light irradiation. The deduced reasons for the differences in the photocatalytic activities of these Bi2WO6 nanostructures are further discussed. (c) 2012 Elsevier Ltd. All rights reserved.