It has been shown previously for electrodeposited Co/Cu multilayers that the single-bath electrodeposition process can be optimized from an electrochemical point of view in order to avoid unwanted Co dissolution and incorporation of Co in the non-magnetic layer during the Cu deposition pulse. In the present work, electrodeposition of Ni-Co/Cu multilayers has been studied to clarify if the same optimization method is appropriate when two magnetic elements are present and if this potential results in the largest giant magnetoresistance (GMR) for the particular alloy system studied. For this purpose, several Ni-Co/Cu multilayers were prepared by varying the deposition potential of the Cu layer. The composition analysis of the deposits showed that the Ni:Co ratio exhibits a minimum as a function of the Cu deposition potential, which can be explained by considering both the dissolution of Co and the mass transport of the reactants. Both the saturation GMR value and the intensity of the satellite peaks in the X-ray diffractograms were highly correlated with the resulting surface roughness of the deposits which was strongly varying with the Cu deposition potential. Higher GMR values, lower saturation fields and more perfect multilayer structure were observed for sufficiently positive Cu deposition potentials only which enabled a partial Co dissolution resulting in a reduced surface roughness. The results draw attention to the complexity of the optimization procedure of the deposition of multilayers with several alloying components. (C) 2012 Elsevier Ltd. All rights reserved.