The paper reports some preliminary results concerning the manufacturing process of CuZnSnSe (CZTSe) and CuInGaSe (CIGS) nanowire arrays obtained by one-step electrodeposition for p-n junction fabrication. CZTSe nanowires were obtained through electrodeposition in a polycarbonate membrane by applying a rectangular pulsed current, while their morphology was optimized by appropriately setting the potential and the electrolyte composition. The electrochemical parameters, including pH and composition of the solution, were optimized to obtain a mechanically stable array of nanowires. The samples were characterized by scanning electron microscopy, Raman spectroscopy, and energy-dispersion spectroscopy. The nanostructures obtained showed a cylindrical shape with an average diameter of about 230 nm and a length of about 3 µm, and were interconnected due to the morphology of the polycarbonate membrane. To create the p-n junctions, first a thin film of CZTSe was electrodeposited to avoid direct contact between the ZnS and Mo. Subsequently, an annealing process was carried out at 500 °C in a S atmosphere for 40 min. The ZnS was obtained by chemical bath deposition at 95 °C for 90 min. Finally, to complete the cell, ZnO and ZnO:Al layers were deposited by magnetron-sputtering.