A polycrystalline BiFeO3 film on Pt/Ti/SiO2/Si was fabricated using the spin coating technique. The film shows diode-like characteristics with and without poling measured under dark conditions. However, it exhibits a switchable photovoltaic effect with light illumination under poled conditions. The measured photovoltaic effect revealed an open circuit voltage of ∼0.47 V and a short circuit current of 3.82 μA/cm2 under the illumination of 165 mW/cm2 irradiance. The studies clarified the dominant role of the depolarization field rather than the interface in the photovoltaic characteristics of the BiFeO3 film. Significantly, the photo-capacitance effect was demonstrated with a substantial enhancement in capacitance (∼45%) in Au/BiFeO3/Pt geometry, which could open up a new window for BiFeO3 applications. © 2017 Author(s).