Different morphologies of monoclinic BiVO4 with smaller size were hydrothermal synthesized by simply adjusting the amount of surfactant (polyvinyl pyrrolidone PVP K30) added. The detailed field emission scanning electron microscope (FESEM) analysis revealed that the amount of PVP added could significantly affect the morphology and size of BiVO4. Their photocatalytic activities were evaluated by the decolorization of methylene blue (MB) aqueous solution under visible-light irradiation (lambda > 400 nm), and the as-prepared sample with well-assembled flower-like morphology showed a much higher photocatalytic activity due to larger specific surface area and higher separation efficiency of photo-induced carriers. The relationship between the behavior of photo-induced carriers and photocatalytic activity was studied using the surface photovoltage spectroscopy (SPS) and corresponding phase spectra. (C) 2011 Elsevier B. V. All rights reserved.