Cobalt and iron(II) hexachloroclathrochelates with apical aliphatic and aromatic substituents were synthesized and characterized using cyclic voltammetry. The obtained clathrochelate-based systems were impregnated on the surface of carbon paper and tested as cathode electrocatalysts in water electrolysis cell with proton exchange membrane (PEM). Both the cyclic voltammograms and the current voltage performances of membrane-electrode assemblies suggested that these cage complexes can be successfully implemented in PEM water electrolyzers and used as efficient electrocatalysts for hydrogen evolution. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.