We investigated the morphology of electrodeposited copper (Cu) onto self-assembled gold nanoparticles (Au NPs) modified highly oriented pyrolytic graphite electrode. A well organized and dense superstructure of Cu dendrites was prepared. By controlling the temperature, polyhedral particles were obtained. The mechanisms behind the formation of the superstructure and morphologies are analyzed and discussed based on the results of FEGSEM, XRD and X-ray photoelectron spectroscopy (XPS). The influence of self-assembled Au NPs template and Cu surface modification with dodecanethiol was discussed. (C) 2013 Elsevier Ltd. All rights reserved.