The aim of this study was to investigate the performance of anion exchange membranes in the electrochemical hydrogen evolution process, which is an important issue in the context of the development of sustainable hydrogen technologies. Fumasep FAA-3-PK-130 and PiperION membranes (40 µm) were used, their properties enabling operation in 1 M NaOH solution at room temperature. The cathodes employed were 304 stainless steel and a nanostructured Co-Ni alloy coating obtained by cobalt and nickel co-deposition. The nanostructured coating enabled resistance reductions of 25.50% and 36.61% for FAA-3-PK-130 and PiperION, respectively. Comparative analysis showed that PiperION exhibited lower resistance but also lower conductivity than FAA-3. Membrane thicknesses were examined after activation to the OH– form. PiperION demonstrated higher liquid absorption, with a swelling ratio of 42.50%, compared to 32.31% for FAA-3. Owing to its advanced polymer backbone, PiperION offers lower resistance and improved anion transport selectivity, while maintaining high stability in alkaline environments. These studies allowed us to evaluate the properties of modern AEM membranes under alkaline conditions and compare their potential for use in hydrogen electrolysis.