Benzylamine catalytic effect on the cathodic hydrogen evolution in acid aqueous solution has been studied on copper electrode. Experimental results obtained by voltammetric techniques emphasize that the presence of benzylamine in 1 M sulfuric acid solution enhances the hydrogen evolution reaction (HER). In such a solution, benzylamine is protonated and exists as benzylammonium cation. Kinetic parameters of HER have been determined, observing a significant increase of the exchange current in the presence of benzylamine. Also, a decrease of the cathodic transfer coefficient has been noticed. Activation energy for HER has been computed on the basis of the Arrhenius plots. In the presence of benzylamine the activation energy was 33.0 kJ mol(-1), whereas without benzylamine a greater value was obtained: 94.6 kJ mol(-1). The catalytic effect of benzylamine was confirmed by electrochemical impedance spectroscopy. The considerable diminution of the double layer capacity is a valid proof of the strong adsorption of benzylamine at the Cu - sulfuric acid solution interface, while the reduction of the charge transfer resistance is a symptom of the enhancement of HER. Ab initio molecular modeling of benzylammonium ion showed that, due to a high value of the dipole moment, the molecules are oriented in the most favorable position for the charge transfer reaction, i.e., with the protonated amino group facing toward the electrode. Copyright (c) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.