This study reports on preliminary experiments which are required to define the experimental conditions for depositing CoSb3 thin films by the electrochemical atomic layer epitaxy (EC-ALE) method. The underpotential deposition (UPD) of cobalt and antimony on polycrystalline gold substrates has been investigated by means of cyclic voltammetry, anodic potentiodynamic scanning and coulometry. The UPD of Sb on Co-covered Au and of Co on Sb-covered Au have also been studied and compared to those obtained on bare Au substrate. The UPD potential values for both Co and Sb are reported in this paper, and owing to the flexibility of the EC-ALE equipment, new insights on the Co UPD on gold substrate are presented. This study shows that the subsequent alternate deposition of Co and Sb monolayers is feasible and thus that the EC-ALE method can be used to elaborate CoSb3 thin films. (C) 2014 Elsevier B.V. All rights reserved.