A CTAB-assisted microwave hydrothermal method was used to synthesize BiVO4 photocatalysts with different shapes. The obtained products were characterized by powder X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), UV-vis diffuse reflectance spectroscopy (DRS). The results showed that the monoclinic phase BiVO4 polyhedron was formed via a tetragonal zircon-type BiVO4 precursor. UV-vis diffuse reflectance spectra showed a great shift to longer wavelengths in the visible region for the monoclinic phase BiVO4 samples compared to the BiVO4 precursor. The photocatalytic activity of the sample was investigated for the liquid phase photocatalytic degradation of RhB under visible light irradiation (λ>420nm). The effects of different reaction times on the photocatalytic activity of BiVO4 had also been investigated, and the highest efficiency was observed when the sample was prepared at 140 °C for 30min.