Urchin-like tungsten oxide hydrate (WO 3 ·H 2 O) hollow spheres were successfully synthesized via a selfsacrifice template method at low temperature. The effects of reaction parameters on the preparation were studied in solution. The growth mechanism was also proposed on the basis of experimental results. In addition, the acid amount and temperature have important effects on size control of the as-obtained samples. The achieved nanoarchitectures have typical diameters of 4-6 μm with nanoflakes of several nanometers at surface. Crystal structure, morphology, and composition of final nanostructures were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Degradation experiments of organic contaminant were also performed on samples of hollow spheres and walnut-like structures under visible-light illumination. Hollow sphere sample exhibited better photocatalytic capability than walnut-like sample. Possible mechanism was studied for WO 3 ·H 2 O assisted photocatalytic degradation of organic contaminant under visible light.