The intermetallic phases along the Pt–Mo phase diagram, singly or in combination with specific ionic activators, have been investigated as cathode materials for the production of hydrogen by electrolysis from water KOH solutions in an attempt to decrease energy consumption. The influence of ionic activators (activating compounds) on energy consumption was significant. The intermetallic phases, as cathode materials, were activated by the surface deposition of activating compounds from electrolyte. The influence of these cathode materials on the electrolytic evolution of hydrogen was discussed in the context of transition metals features and their electronic configuration.