The performance of a cation-exchange membrane (CEM) used for recovering zinc from real spent pickling baths is studied in this work. These spent baths contain high amounts of ZnCl2 and FeCl2 in aqueous HCl media. The results obtained with this membrane are compared with those obtained with an anion-exchange membrane (AEM) treating the same effluent. The effect of the presence or absence of initial zinc in the cathodic compartment is also studied. The absence of initial zinc in the cathodic compartment in the CEM experiments permits iron codeposition. Furthermore, the results obtained with the CEM are worse than those obtained with the AEM for all the figures of merit. This fact shows the need of filling the cathodic compartment with a synthetic zinc solution. The presence of zinc in the cathodic compartment from the beginning of the electrolysis not only inhibits iron codeposition but also favors zinc deposition as the hydrogen evolution reaction becomes a secondary reaction, improving by this way the results of all the figures of merit of the reactor with the CEM. A deep study about the effect of the applied current and the concentration of the synthetic zinc solution placed in the cathodic compartment permits to reach the equilibrium between the zinc transferred through the membrane and that deposited on the cathode. Therefore, the synthetic cathodic zinc is not consumed at any time. Moreover, under this circumstances iron codeposition is also avoided. (C) 2014 Elsevier B.V. All rights reserved.