A simple two step solution-based method was applied to fabricate CuO-ZnO heterostructured nanowire (NW) arrays. First, ZnO nanowires were grown on a Si substrate using the ammonia solution hydrothermal reaction. Afterwards, flower-like CuO crystals were photochemically deposited on the tip of the ZnO NWs, using ultraviolet (UV) light (312 nm wavelength) irradiation at room temperature. The morphology of the CuO was controlled by reaction time, density of ZnO NWs, and concentration of the solution. Because the deposited CuO is p-type and has narrow band gap properties, CuO-ZnO heterostructured NWs exhibited a stable p-n junction property and good ability to absorb visible light. Through investigation of UV light-triggered reaction phenomena, we found that the production of OH(-) from the photocatalytic process on the surface of ZnO NWs plays a critical role in the CuO deposition mechanism.