Zn-Co alloy electrodeposition from chloride baths containing different Zn2+/CO2+ ratios was investigated by cyclic voltammetry and anodic linear sweep voltammetry using a Pt electrode. The peaks were attributed by means of EDX analysis, SEM and TEM observations performed on some alloys potentiostatically deposited. In the range of potential where zinc deposits underpotential, cyclic voltammetry showed acomplex cathodic peak with one maximum and two shoulders, correlated with the deposition of different cobalt rich alloys. Up to four anodic peaks, two correlated with zinc oxidation from eta and gamma phases and two correlated with oxidation of solid solutions of zinc in cobalt, were observed. ALSV and TEM indicated that the remarkable increase in Zn content of the alloy, which occurs with a strong inhibition of the process at potentials more negative than that of the cathodic peak and more positive than the bulk deposition potential of zinc, is due to the deposition of gamma phase. No inhibition of the alloy deposition process was observed with very low concentrations of zinc (< 0.015 M) in the bath containing 0.19 M Co2+. (c) 2005 Elsevier Ltd. All rights reserved.