Nanoflake-based flower-like and hollow microsphere-like hydrated tungsten oxide architectures were selectively synthesized by acidic precipitation of sodium tungstate solution at mild temperature. Several techniques, such as X-ray diffraction, scanning electron microscopy, thermogravimetric-differential thermalgravimetric analysis, transmission electron microscopy, and Brunauer-Emmett-Teller N-2 adsorption-desorption analyses, were used to characterize the structure and morphology of the products. The experimental results show that the nanoflake-based flower-like and hollow sphere-like WO3 center dot H2O architectures can be obtained by changing the concentration of sodium tungstate solution. The possible formation process based on the aggregation-recrystallization mechanism is proposed. The corresponding tungsten oxide three-dimensional architectures were obtained after calcination at 450 degrees C. Finally, the obtained WO3 three-dimensional architectures were used as photocatalyst in the experiments. Compared with WO3 microflowers, the as-prepared WO3 hollow microspheres exhibit superior photocatalytic property on photocatalytic decomposition of Rhodamine B due to their hollow porous hierarchical structures. (c) 2012 Elsevier Ltd. All rights reserved.