Vertical p-ZnO:Cu/n-ZnO homojunction nanowires (NWs) and whole ZnO:Cu NWs were synthesized on a ZnO thin film/glass substrate by a furnace at 600 °C with 1700 °C hotwire assistance. According to the ZnO:Cu NW investigation, the energy-dispersive X-ray (EDX) spectrum indicates that the Cu content is 3.01 atomic %. The X-ray diffraction (XRD) peaks of ZnO:Cu NWs shift toward larger angles with increasing amounts of doped Cu. The Cu dopant enhanced the photoluminescence (PL) green-band peak and decreased the conductivity of the NWs, as measured by I-V. The gas sensing measurement and Hall effect verified that all ZnO:Cu NWs were p-type. In this study, transmission electron microscopy (TEM) and EDX mapping images revealed that the majority of the Cu element is located at the top of the p-ZnO:Cu/n-ZnO NW. The high-resolution transmission electron microscopy (HRTEM) image of the p-ZnO:Cu region shows that the NWs are [0001] growth-oriented, with lateral surfaces enclosed by (1̅101) planes. The I-V curve of p-ZnO:Cu/n-ZnO NWs displays the characteristics of normal rectifying diodes. The photocurrent under ultraviolet (UV) exposure was around 6 times higher than the dark current at the reverse bias of -5 V.