The to study of the total oxide (SiO(2)+SiO(x)) thickness, SiO(2) and SiO(x) (e.g. Si(2)O, SiO, Si(2)O(3)) thicknesses on Si(100) crystalline substrate with take-off angles ranging from 30 degrees to 80 degrees has been carried out by spectrometric method. The d(s) X-ray Photoelectron Spectroscopy (XPS) thicknesses were compared with d(EL) thicknesses obtained by fitting the Spectroscopic Ellipsometry (SE) spectra. A qualitatively good correlation is revealed. However, from these estimations of film thicknesses it results that ellipsometry analysis cannot be as accurate as in XPS evaluation. This is due to uncertainty of used optical constants as well due to very thin oxide films used in this work.