The preparation of Zn deposits has been performed by galvanostatic pulsed electrolysis, from acidic zinc sulphate solutions, on a stainless steel substrate. The influence of the surfactants (cetyl trimethyl ammonium bromide (CTAB), sodium dodecyl sulphate (SDS) and octylphenolpoly(ethyleneglycolether)(n), n=10, Triton X-100) on the voltammetric behaviour, structural and morphological characteristics of the deposits have been investigated. The characterization of the samples was made by X-ray diffraction (XRD) and scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM/EDS). The experimental data shows that the presence of surfactants affects the zinc deposition process. The electrodeposits are mainly composed by Zn with different texture, crystal shape and size (grain size ranging from 40 to 20 nm). The obtained results led us to conclude that the Zn 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 the increase on the overpotential deposition as the electrochemical studies confirm. The XRD results show that the deposits prepared, in the absence of surfactant and in the presence of SIDS, contain ZnSO4 and Zn4SO4(OH)(6) as oxidation products. ZnO is also detected on the deposits obtained in the presence of CTAB and Triton X-100. (C) 2005 Elsevier Ltd. All rights reserved.