In this study, copper oxide (CuO) thin film/silicon (Si) nanowire heterojunctions have been fabricated and their optoelectronic performances have been investigated. Vertically aligned n-type Si nanowires have been fabricated using metal-assisted etching (MAE) technique. CuO thin films were synthesized by the sol-gel method and deposited onto the nanowires through spin-coating. Fabricated nanowire heterojunction devices exhibited excellent diode behaviour compared to the planar heterojunction control device. The rectification ratios were found to be 105 and 101 for nanowire and planar heterojunctions, respectively. The improved electrical properties and photosensitivity of the nanowire heterojunction diode was observed, which was related to the three-dimensional nature of the interface between the Si nanowires and the CuO film. Results obtained in this work reveal the potential of Si nanowire-based heterojunctions for various optoelectronic devices.