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Various micro/nanostructured WO 3 ?0.33H 2 O crystallites were successfully controlled by employing microwave heating under different conditions. By using X-ray diffraction, scanning electron microscopy, transmission electron microscopy and high resolution transmission electron microscopy, the phase and morphology of the products were identified. Comparing the as-prepared crystallites under conventional and microwave heating processes found that microwave heating may play a crucial role to initiate the oriented growth of orthorhombic WO 3 ?0.33H 2 O micro/nanostructures. Moreover, these oriented structures exhibit clearly improved photocatalytic activity over the structures prepared under the conventional heating process. By applying the multi-site complexation model, the improved photocatalytic properties were found to relate to the exposure of high surface acidity orthorhombic WO 3 ?0.33H 2 O crystallites, which originate from the oriented growth of microstructures prepared under the microwave heating process.

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