We report a growth of p-CuO nanowire arrays with a simple thermal oxidation and a fabrication of nanowire-based heterojunctions by coating the p-CuO nanowire arrays in an n-ZnO layer through a thermal decomposition method. Their optoelectronic properties and photovoltaic performance were investigated. Compared with the conductance in the dark, a 154% increase in photoconductance was obtained under a white light illumination of 100 mW/cm2. The heterojunctions exhibit an obvious photocurrent increment of 0.264 mA under the illumination of 141 mW/cm2. After annealing the heterojunctions at 100°C for 25 min, a larger open-circuit voltage of 0.37 V was obtained, the short-circuit current density increase to 0.63 mA/cm2 from original 0.49 mA/cm2. The overall power conversion efficiency is 0.1%.