Zinc electrodes were polarized cathodically at moderate overpotentials in NaCl 0.6 M solutions under potentiostatic conditions for 7 to 17 hours at room temperature. Corrosion products were characterized by using optical microscopy, XRD, Raman microscopy, XPS, and FIB-SEM. Close to the open-circuit potential, the corrosion products were formed by simonkolleite and the electrochemical response exhibits anodic features. At more negative potentials, the current density remains cathodic throughout the polarization and the deposits on the electrode surface consist almost solely of ZnO. The soluble zinc species necessary for ZnO deposition originate from localized dissolution of the substrate in the form of pits. This effect is assigned to the strong alkalinization of the surface due to oxygen reduction. Despite developing greater surface area than bare zinc substrates, the nanostructured ZnO deposits reduced the cathodic activity.