Zinc oxide (ZnO) films were deposited onto Si to form n-ZnO/p-Si heterojunctions. Under the illumination of by both ultraviolet (UV) light and sunlight, obvious photovoltaic behavior was observed. It was found that the conversion efficiency of the heterojunctions increased significantly with increasing thickness of the ZnO film, and the mechanism for light-harvesting in the heterojunctions is discussed. The results suggest that ZnO films may be helpful to increasing the harvesting of UV photons, thus decreasing the thermalization loss of UV energy in Si-based solar cells.