Effects of two additives, thiourea and saccharin, oil copper electrodeposition from acid sulphate solutions were investigated by different electrochemical methods (cyclic voltammetry, chronoamperometry, and electrochemical quartz crystal microbalance) as well as by different observation techniques (scanning electron microscopy and atomic force microscopy). The morphology of copper coating obtained with thiourea leads to a smooth and bright deposit whereas it is only slightly modified by saccharin. The electrochemical reactions of copper electrodeposition were modified by the formation of complexes between thiourea and copper. However. in presence of saccharin, the kinetics and morphology of copper coating remain unchanged. From X-ray photoelectron spectroscopy analysis, thiourea was found to react with copper or copper ions by strong bond formation between the sulphur atoms of thiourea molecule and copper. This is the evidence of the adsorption of thiourea oil the coating, Moreover, the thiourea action starts in the initial stages, allowing a homogeneous nuclei size and a large nuclei density. Finally, the nucleation mechanism of electrodeposition appears to be modified according to the additives Used. (C) 2008 Elsevier Ltd. All rights reserved.