In the present paper a novel approach to control size and shape of deposited copper particles and nanoparticles from industrial electrolytes at the ultramicroelectrodes (UME) is presented. The copper nanopowders were pulse deposited on different metallic substrates from copper electrorefinery electrolytes. The SEM and electrochemical measurements showed that the morphology and structure of copper deposit can be precisely controlled by using different substrates and kind of chronoamperometric pulses. By choosing appropriate UME metal it is possible to get either the growth of copper spherical clusters, nano-wires or smooth flat films of copper. It was found that increasing deposit potentials produces smaller nuclei and higher nuclei copper population density. The kinetics and mechanism of copper nucleation was studied as well. It should be noted that very high nucleation rates and apparent cathodic current densities can be obtained at the ultramicroelectrodes. (C) 2009 Elsevier B.V. All rights reserved.