The present work investigates the behavior of nanostructured electrodes consisting of an array of nanowires of NiFe alloy in KOH + 0.5 M NaCl solution. The aim is to explore the possibility of using these electrodes for hydrogen production by seawater electrolysis. Seawater splitting requires a highly selective electrode on the anode side, where the evolution of molecular chlorine or the formation of other active chlorine compounds can compete with the oxygen evolution reaction. Nanostructured electrodes, obtained by template electrosynthesis, were tested at room temperature in KOH + 0.5 M NaCl solution, and the results were compared with those obtained in pure KOH. The results showed that the presence of NaCl does not affect the electrocatalytic behavior of the nanostructured NiFe alloy. Furthermore, the chemical–physical characterizations carried out after the long-term galvanostatic tests, have shown that the nanostructured electrodes are also stable in terms of morphology and composition. In addition, the solution used to perform the long-term galvanostatic tests was analyzed to investigate the possible formation of chlorine compounds. The absence of these compounds, together with the measured potential value measured for the oxygen evolution reaction, which was always lower than the thermodynamic redox potential for the hypochlorite formation reaction, leads us to conclude that these electrodes are potentially suitable for seawater electrolysis.