In this study, nickel (Cu/Ni), iron (Cu/Fe) and nickel-iron (Cu/NiFe) composite coatings with various chemical compositions were electrochemically deposited on a copper electrode and characterized using cyclic voltammetry (CV), atomic absorption spectroscopy (AAS), scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques in view of their possible applications as electrocatalytic materials for the hydrogen evolution reaction (HER) in an alkaline medium. The electrocatalytic activity of the coatings for the HER was studied in 1 M KOH solution using cathodic current-potential curves and electrochemical impedance spectroscopy (EIS) techniques. The presence of nickel along with iron increases the electrocatalytic activity of the electrode for the HER when compared to nickel and iron coatings individually. The HER activity of the composite coatings depends on the chemical composition of the alloys. The Cu/NiFe-3 electrode (with a molar concentration ratio of Ni2+:Fe2+ of 4:6 in the plating bath) was found to be the best suitable cathode material for the HER in an alkaline medium under the experimental conditions studied. Furthermore, the electrocatalytic activity of the Cu/NiFe-3 electrode for the HER was tested for extended periods of time in order to evaluate the change in the electrocatalytic activity of the electrode with operation time. The HER was activation controlled and has not been changed after electrolysis. A constant current density of 100 mA cm(-2) was applied to the electrolysis system, and the corrosion behavior of the Cu/NiFe-3 electrode was investigated after different operation times using EIS and linear polarization resistance (LPR) techniques. For comparison, the corrosion behavior of a Cu/NiFe-3 electrode to which current was not applied was also investigated. The corrosion tests showed that the corrosion resistance of the Cu/NiFe-3 cathode changed when a cathodic current was applied to the electrolysis system. (C) 2009 Elsevier Ltd. All rights reserved.