In this work, tungsten oxide (WO3) with three-dimensional flower-like and wheel-like architectures, based on the spontaneous aggregation of one-dimensional nanorods, were successfully fabricated by adjusting the pH of the precursor solution. The influence of pH on the morphologies of WO3 was systematically studied, and the different WO3 architectures were used to photocatalytically degrade rhodamine B. The kinetic features of photoinduced charges of as-prepared WO3 have been investigated by surface photovoltage spectroscopy and transient photovoltage techniques in detail. WO3 with wheel-like and flower-like structures possess the higher charge separation efficiency and the lower recombination rate of photoinduced charges, resulting in higher photocatalytic activity for the degradation of RhB.