In this study, a ZnO seed layers was fabricated on a silicon substrate by a sol–gel method, and vertically aligned Co/Ca-codoped ZnO (CCZ) nanowire arrays were prepared on the ZnO seed layer by a hydrothermal method. The Co and Ca were doped to improve the structural, photoluminescence, and magnetic properties of CCZ nanowire arrays. The CCZ and undoped ZnO nanowires exhibited the c-axis orientation and single polycrystalline phase with the wurtzite hexagonal structure of P63/mc. The photoluminescence spectrum showed that the UV emission (about 374 nm) of the CCZ nanowires decreased and the green light emission (about 513 nm) increased compared with those of undoped ZnO nanowires. From the hysteresis curve, the magnetic field dependence of the magnetization as a function of magnetic field showed the existence of ferromagnetism for CCZ and undoped ZnO nanowires. The saturation magnetization of the CCZ nanowires is 0.46 emu/g, which is better than that of undoped ZnO nanowires (0.22 emu/g). These results demonstrate the properties of CCZ nanowire arrays with potential applications in optoelectronics and spintronics.