A two-step hydrothermal method was applied to create WO3/NiWO4 composite films on conductive glass (FTO). The structure and morphology of WO3/NiWO4 composite films were characterized by XRD and SEM. The photoelectric properties of WO3/NiWO4 composite films were analyzed by UV-VIS, photocurrent test, photoelectrocatalytic test and AC impedance test. The analysis results indicate that the WO3/NiWO4 composite film has better light absorption characteristics, photocurrent density and photoelectrocatalysis activity than WO3 film, and the WO3/NiWO4 composite film with 3 hours hydrothermal reaction has the best photoelectrochemical properties. The photocurrent density of WO3/NiWO4-3h was 1.94mA/cm2 at 1.4V(vs. Ag/AgCl), and the photoelectrocatalytic efficiency of WO3/NiWO4-3h for methylene blue solution was 57.1% for 210min. The AC impedance diagram reveals that the charge transfer resistance of WO3/NiWO4 film is less than that of WO3 film, which corresponds to improved photoelectrochemical properties.