We report a selective growth method of copper (Cu) nanoparticles electrodeposition on hexagonally patterned electrodes by self-assembled gold nanoparticles (Au NPs). The self-assembled Au NPs behave as an electrocatalysis seed layer for Cu electrodeposition. Au NPs activate the inhibited site (without defects) of bare HOPG for the same applied potential. The dodecanethiol ligands around the Au NPs fix the distance between them and avoid the coalescence processes in the first electrodeposition stage. The hexagonal periodicity of the Au NPs is well reproduced. This nanostructuring method provides a promising way to control the electrodeposits growth into ordered structure at nanometer resolution. (C) 2013 Elsevier B.V. All rights reserved.