An electrochemical method for preparation of bimetallic nanoparticles is described. Gold nanoparticles were first self-assembled on gold film electrode by 1,6-hexandithiol via Au-S bond. A [PtCl(6)](2-) layer was then adsorbed onto the prepared gold nanoparticles and Au@Pt nanoparticles could be obtained through pulsed potentiostatic reduction. The structure and nature of the resulting Au@Pt nanoparticles were characterized by scanning electron microscopy, transmission electron microscopy, UV-visible spectroscopy, cyclic voltammetry and electrochemical impedance spectroscopy techniques. The electrocatalytic activity of Au@Pt bimetallic nanoparticles toward hydrogen evolution reaction (HER) has been investigated. The kinetic constants for HER were comparatively investigated for different modified electrodes by hydrogen evolution voltammetry. (C) 2009 Elsevier B.V. All rights reserved.