Ni-Mo-Cu alloy coating electrode was prepared on copper substrate by constant current electrodeposition and characterized by scanning electron microscopy (SEM) and X-ray diffractometry (XRD). The electrochemical characterization for hydrogen evolution reaction (HER) was investigated by cyclic voltammetry (CV) curves, linear sweep voltammetry (LSV) curves and electrochemical impedance spectroscopy (EIS) techniques. Parameters affecting the electrocatalytic activity for the HER are systematically investigated. Results show the Ni-Mo-Cu coating by the introduction of Cu has a rough and cauliflower-like structure and presents a most efficient activity for HER in comparison with binary Ni Mo electrode. Its remarkably enhanced catalytic activity is attributed to the high surface area as well as synergistic interaction between Ni, Mo and Cu. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.