Monoclinic crystal bismuth vanadate (BiVO4) was synthesized by the high temperature solid state reaction after ball milling the materials of Bi2O3 and V2O5. The influences of sintering times on the crystal phases and structures of BiVO4 powders were studied through the XRD、FTIR characterization. Fe-doped BiVO4 was prepared by doping ferric chloride to pure monoclinic crystal BiVO4 to improve the photo absorbance performance of BiVO4 and to promote the isolation of photo-induced carriers. Visible light activity of BiVO4 and Fe-doping BiVO4 were characterized using the UV-diffuse reflectance spectroscopy. The electrochemical behaviors of BiVO4 and Fe-doping BiVO4 were investigated under the condition of avoiding light or under light.