Hierarchically flower-like tungsten trioxide assemblies were fabricated on a large scale by a simple hydrothermal treatment of sodium tungstate in aqueous solution of nitric acid. The as-prepared samples were characterized by X-ray diffraction, scanning electron microscopy and N-2 adsorption-desorption measurements. The photocatalytic activity was evaluated by photocatalytic decolorization of rhodamine B aqueous solution under visible-light irradiation. It was found that the three-dimensional tungsten trioxide assemblies were constructed from two-dimensional layers, which were further composed of a large number of interconnected lathy nanoplates with different sizes. Such flower-like assemblies exhibited hierarchically porous structure and higher visible-light photocatalytic activity than the samples without such hierarchical structures due to their specific hierarchical pores that served as the transport paths for light and reactants. After five recycles for the photo degradation of RhB, the catalyst did not exhibit any great loss in activity, confirming hierarchically flower-like tungsten trioxide was stability and not photocorroded. This study may provide new insight into environmentally benign preparation and design of novel photocatalytic materials and enhancement of photocatalytic activity. (C) 2009 Elsevier B.V. All rights reserved.