The segregation of Pb on model binary AlPb alloys, containing 20 and 50 ppm Pb, as a result of heat-treatment in air at 600 degrees C and its influence on electrochemical properties have been studied. Enrichment of metallic Pb, concentrated toward the oxide side of the oxide-metal interface, was confirmed by X-ray photoelectron spectroscopy. Transmission electron microscopy revealed a nearly continuous nanometer-scale Pb film at the oxide-metal interface. Significant anodic activation of the AlPb alloy surface in relation to pure Al in chloride media is attributed to the Pb film destabilizing the thermal oxide. The degree of activation was limited by the surface coverage of the film, and discrete Pb particles in the oxide did not contribute to the activation. After initiation at certain grain boundaries and discrete sites on grain bodies, corrosion in the active state spread nearly two-dimensionally as the Pb film on the corroded sites was destroyed as a result of corrosion, and corroded sites repassivated. The formation of the gamma-Al2O3 thermal oxide during heat-treatment was thus crucial in the formation and existence of the Pb film wetting the metal surface. (c) 2006 The Electrochemical Society.