Monoclinic BiVO4 photocatalysts with porous structures were synthesized by a two-step approach without assistance of any templates. The as-prepared samples were characterized by X-ray diffraction pattern (XRD), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET), ultraviolet–visible (UV–vis) diffuse reflectance spectroscopy (DRS), photocurrent responses, and electrochemical impedance spectra (EIS). It is found that the as-prepared BiVO4 samples had a porous structure with aperture diameter of 50–300 nm. Moreover, the BET specific surface area of the porous BiVO4-200 °C sample reaches up to 5.69 m2/g, which is much higher than that of the sample of BiVO4 particles without porous structure. Furthermore, a possible formation mecha...