The effect of the electrolyte on the hydrogen electrode reaction (HER) has been investigated. As a starting point, we centered our studies on the Volmer reaction in alkaline media - H2O + e(-) -> H-ad + OH- - on a Pt(111) surface. The adsorption process of the reaction intermediate Had was investigated by quantum chemical calculations. Our analysis focused on the interaction of the OH and the Had with the electronic bands of the metal electrode. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.