Electrochemical stripping techniques were used to characterize zinc + nickel alloys obtained from an ammonium bath. Different electrochemical and ex situ techniques were applied to ensure the selective oxidation of the alloy components. The voltammetric peaks obtained at more negative potentials during the oxidation process were due to the dissolution of the less noble component (zinc) from the different phases of the alloy, while the peak at more positive potentials corresponded to the oxidation of nickel. Moreover, the possibility of a phase transition during the oxidation process of zinc + nickel alloys is also discussed.