This work reports the research carried out by studying aliquots extracted at different axial coordinates from Three Way Catalyst (TWC) monoliths aged under real traffic conditions. Our study focused on the catalytic properties and on several chemical and physical effects caused in the Front and Rear monolith washcoat surfaces by vehicle aging after 60,000 km. Regarding the catalytic properties, all the used aliquots showed poorer activity than their corresponding fresh counterparts. The strongest deactivation was detected for NO and hydrocarbon conversion. CO conversion was less affected and the Rear monolith was as deactivated as the Front one. The characterisation techniques (TXRF, N-2, adsorption-desorption isotherms, XRD and H-2-TPR) detected - (i) the deposition of P, Zn and Pb; (ii) the formation Of CePO4 on account of the Ce from the washcoat; (iii) thermal sintering; (iv) inhibition of the reducibility of Ce oxides -as the main effects brought about by vehicle aging conditions. The deactivation observed at the beginning of the Front monolith was the result of a combination of the former effects. When moving downstream to higher axial coordinates, Pb accumulation and the loss of specific area appeared to be the only probable sources of deactivation. (c) 2005 Elsevier B.V. All rights reserved.