This work presents a study of the selective electrowinning of gold from thiosulfate electrolyte, taking into account difficulties related with low gold concentration and metal impurities that usually limit gold recovery. The cathodic and anodic processes were evaluated in a potential window where gold and copper reduction and the oxidation of thiosulfate and Cu (I) species occurs. Three materials with different reactivity were evaluated as cathode: Pt, Ti and DSA. It was possible to define the effect of each material in the electrochemical reactions involved and to identify three potential regions where selective electrodeposition happens: the first one involves selective deposition of gold, the second accounts for the co-deposit formation of copper and gold and the last one for the massive copper electrodeposition. The use of DSA as cathode electrode showed an intermediate electrochemical behavior between Pt and Ti and good selectivity. For these reasons DSA is proposed as a good cost/benefit option for gold electrowinning process from thiosulfate solutions.