Interaction of silicon with cerium oxide was studied by photoelectron spectroscopy using two model systems CeOx/Si(1 1 1) and Si/CeO2(1 1 1)/Cu(1 1 1) which can be used for fundamental studies in the field of microelectronics and heterogeneous catalysis. The interaction was found to be strong and lead to a formation of cerium silicate films of the proposed stoichiometry Ce4.67Si3O13. Their maximum thickness was limited by diffusion of silicon. Beside silicate other compounds were growing on the surface - SiO2, Si2O, Si, and CeO2. The assignment of the formed species is based on the interpretation of photoemission spectra involving the measurements of various reference O/Si and Si-O/Cu systems. (C) 2012 Elsevier B.V. All rights reserved.