Segregation of Pb as a nanofilm between the thermal oxide and the metal substrate as a result of high temperature heat-treatment is known to activate aluminum alloys anodically in chloride solution. The relationship between the oxidation peaks in the polarization curve and corrosion morphology was investigated by the use of a video technique during electrochemical polarization. A model binary Al-Pb alloy containing 20 ppm Pb, which was annealed at 600°C, showed two oxidation peaks at -0.95 and -0.88 V SCE. The video measurements revealed superficial etching of the surface by selective oxidation of the aluminum metal twice, followed each time by repassivation, as the two oxidation peaks were resolved during anodic potentiodynamic sweep. Ex situ scanning and transmission electron microscopy of the corroded specimens indicated that the first layer of etching followed the Pb film and undermined the thermal oxide, which remained attached to the metal surface at discrete locations, thereby forming a crevice. The second layer of attack was caused by crevice corrosion of the aluminum substrate in the crevice formed by the preceding oxidation process, which resulted in the removal of the attached thermal oxide film. The exposed aluminum substrate started to pit as the pitting potential was finally exceeded.