Bi2MoO6 films on ITO glass substrates were prepared from amorphous complex precursor by dip-coating technique. The relationships between conditions of preparation, structures, morphologies and photoelectrochemical properties of Bi2MoO6 films were investigated by using scanning electron microscope (SEM), X-ray diffraction (XRD), laserRamanspectroscopy (LRS), diffuse reflectance spectroscopy(DRS), photocurrent actioncurves, andincident photon-to-current conversion efficiency (IPCE). Bi2MoO6 films prepared at 500 ℃ for 1 h were γ-Bi2MoO6 phase, and Bi2MoO6 nanoparticles grew along (131) plane. The thickness of the films obtained was about 69 nm. The size of the Bi2MoO6 nanoparticles was increased with rising calcination temperature and extention of calcination time, in addition γ-Bi2MoO6 changed into β-Bi2MoO6 and γ’-Bi2MoO6 at 525 ℃. Bi2MoO6 films had visible-light response, and detectable photocurrent was generated under the visible-light (λ>400 nm) irradiation. The IPCE of the optimized Bi2MoO6 films was 2.14% at 400 nm. The photocurrent density and IPCE could be controlled by modifying the surface structure of Bi2MoO6 films, which could be achieved by changing the preparation conditions.