CeO2 is an interesting buffer layer material for the growth of YBa(2)Cu(3)O(7-)delta overlayers on Si in devices, with the aim of preventing heat-diffusion due to its excellent lattice matching with Si and YBa(2)Cu(3)O(7-)delta. Epitaxial CeO2-films have been synthesised on Si(lll) by pulsed laser deposition. Stoichiometric changes of the CexOy-film depending on the ambient oxygen pressure during the deposition were studied by X-ray photoelectron spectroscopy. A method is presented for growing a sharp interface between CeO2 and Si(111). The dependence of the inplane orientation of the CeO2 film on the substrate temperature was investigated by X-ray diffraction. The best films, grown at 700 degrees C, showed full width at half maximum of the rocking curve close to 0.1 degrees, but already at room temperature very highly oriented films with less than 0.2 degrees were synthesised.