Zinc substrates were electrochemically oxidized in NaCl solution to produce corrosion patinas. XRD, XPS and Raman analyses enabled the identification of simonkolleite and zinc oxide as the patina constituents. FIB-SEM imaging shows that the upper part of the patinas is a network of simonkolleite nanosheets with an open microstructure that is unlikely to act as a significant barrier for corrosion processes. STEM investigations and Raman mapping measurements reveal the presence of a ca. 20–400 nm thin nanoporous ZnO-rich film below the simonkolleite and covering the zinc substrate. Under potentiostatic conditions, the reduced cathodic activity of the patina-covered zinc electrodes is assigned to this nanoporous ZnO layer.