Interaction of aluminium with cerium oxide was studied by photoelectron spectroscopy of Al/CeO2(1 1 1) and CeO2/Al(1 1 1) model systems. It was found in both cases that metallic aluminium was immediately oxidized, CeO2 was partially reduced and a mixed oxide with cerium present as Ce3+ was formed. The compound is probably cerium aluminate CeAlO3 mixed with Al2O3 or Ce2O3. In both cases the intermixing was limited by the diffusion of aluminium into ceria. The excess of deposited material above this limit formed AlOx and CeO2 overlayers on the top of the mixed oxide + aluminate/CeO2 and mixed oxide + aluminate/Al films, respectively. (C) 2010 Elsevier B.V. All rights reserved.