Intermetallics phases along Mo-Pt phase diagram have been investigated as cathode materials for the production of hydrogen by electrolysis from water KOH solutions, in an attempt to increase the electrolytic process efficiency. These materials were compared with conventional cathodes (Fe and Ni), often used in the alkaline electrolysis, and also with the intermetallic Ti-Pt. An significant upgrade of the electrolytic efficiency using intermetallics in pure KOH electrolyte was achieved in comparison with conventional cathode materials. The effects of those cathode materials on the process efficiency were discussed in the context of transition metal features that issue from their electronic configuration. (c) 2005 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.