An article by Jones et al. [J. Vac. Sci. Technol. B 16, 2686 (1998)] on the epitaxial growth of Si/CeO2/Si(111) structures is commented upon. The area of major disagreement regards the interpretation that the authors propose to explain their x-ray photoemission spectroscopy (XPS) results, specifically the statement that Ce metal segregates to the surface of the overgrown silicon layer as a result of CeO2 decomposition. It is shown that the XPS results can be accounted-for only by assuming that Ce2O3-Like species, and not Ce metal, segregate to the surface. The surface chemistry of Ce-O-Si systems and some methodological aspects associated with their XPS analysis are discussed.