The zinc electrodeposition onto steel substrates in the presence of surfactants with different charged head groups, namely anionic sodium dode-cylsulphate (SDS), cationic dodecyltrimethylammonium bromide (CTAB), and non-ionic octylphenotpoly(ethyleneglycolether)(n), n = 10 (Triton X-100) was studied by cyclic voltammetry. The effect of the switching potential and scanning rate on the deposition process was investigated. The structural characterisation and the chemical composition of the samples prepared potentiostaticaly, in the potential range where the voltammetric cathodic peaks appear, was performed by X-ray powder diffraction (XRD) and by energy-dispersive X-ray analysis (EDS), respectively. The experimental results show that the voltammetric behaviour, namely the deposition potential depends on the presence, nature and concentration of the tested surfactants. Zn deposition occurs at potential values more positive than the estimated equilibrium potential, peak Cl, simultaneously with hydrogen formation. This fact is confirmed by XRD measurements. Zn bulk deposits prepared in the absence of surfactants and in the presence of SDS are more crystalline and with a higher grain size than the ones obtained in the presence of CTAB and Triton X-100. These facts may be justified by an increase on the overpotential deposition as the electrochemical study confirms. (c) 2006 Elsevier Ltd. All rights reserved.