Due to the increased contact area with the electrolyte, nanostructured nickel coatings on the highly developed surface of porous alumina possess enhanced characteristics in cathodic hydrogen evolution reactions. This paper presents the results of studies of the morphology, electronic surface structure, and cathodic properties of such coatings obtained by magnetron sputtering. It was shown that, depending on the porous structure of the substrate, coatings of various morphologies are formed. The optimal parameters of the porous structure for obtaining coatings of hydrogen evolution with maximum efficiency are determined.