The nucleation and growth of copper crystals on a glassy carbon electrode are studied under potentiostatic conditions. Current transients are recorded at different overpotentials and are interpreted in terms of the theory of progressive nucleation and growth under combined charged transfer and diffusion limitations. Data are obtained on the overpotential dependence of the stationary nucleation rate and on the size of the critical copper nuclei. The influence of ion transfer and electron transfer electrochemical reactions taking place prior to and simultaneously with the process of nucleus formation is discussed and their contribution to the total current is accounted for. (c) 2005 Elsevier Ltd. All rights reserved.