The corrosion layers electrochemically formed on the lead-silver/H2SO4+Mn(II) interface were studied through open-circuit potential monitoring, cyclic voltammetry, and chronoamperometry and were characterized by cyclic voltammetry, X-ray diffraction, and scanning electron microscope coupled to an energy dispersive spectrometer to analyze microregions. Mn(II) oxidation reactions take place in the range of 1 < E < 2.2 V vs standard hydrogen electrode. When an oxidation potential pulse of 1.96 V is applied on a lead-silver electrode, different species are formed as the electrolysis time proceeds. This modification can be divided into four stages: at 0 < t < 5 min, Pb3O4 is formed on the metallic lead; this compound favors the formation of alpha-MnO2. At t=5 min, alpha-MnO2 completely covers the surface, generating high current densities. At 5 < t < 60 min, the anodic layer loses its electroactive properties as it grows and MnO4-and delta-MnO2, which are less electroactive than alpha-MnO2, are formed. At t>60 min, the formation of delta-MnO2 predominates, transforming the crystalline surface into an amorphous and nonelectroactive one. Furthermore, the anodic layer is broken, liberating Pb2+ and exposing metallic lead, which is oxidized to PbO2. The Pb2+ released forms PbMn8O16 on the electrode surface and PbSO4 in the bulk.