Preparation of n-ZnO/p-Si heterostructures using solution-synthesized ZnO nanowire films and their photovoltaic characterization is reported. The solution-grown ZnO nanowire film is characterized using scanning electron microscope, electron dispersive x-ray, and optical absorption studies. Electrical and photovoltaic properties of the fabricated heterostructures are studied using e-beam-evaporated aluminum as metal contacts. In order to use transparent contact and to simultaneously collect the photogenerated carriers, sandwich-type solar cells were fabricated using ZnO nanorod films grown on p-silicon and indium tin oxide (ITO) coated glass as ITO/n-ZnO NR/p-Si. The electrical properties of these structures are analyzed from current-voltage () characteristics. ZnO nanowire film thickness-dependent photovoltaic properties are also studied. Indium metal was also deposited over the ZnO nanowires and its effects on the photovoltaic response of the devices were studied. The results demonstrated that all the samples exhibit a strong rectifying behavior indicating the diode nature of the devices. The sandwich-type ITO/n-ZnO NR/p-Si solar cells exhibit improved photovoltaic performance over the Al-metal-coated n-ZnO/p-Si structures. The indium deposition is found to show enhancement in photovoltaic behavior with a maximum open-circuit voltage () of 0.3 V and short-circuit current () of A under ultraviolet light excitation.