In this paper results concerning optical analysis of the SiO2/Si system performed by the combined ellipsometric and reflectometric method used in multiple‐sample modification will be presented. This method is based on combining both the single‐wavelength method and the dispersion method. Three models of the system mentioned, i.e. the model of the substrate and the layer with the smooth boundaries, the same model with a transition layer and the model of the substrate and the layer with rough boundaries, will be used to interpret the experimental data. The spectral dependences of the optical constants of silicon and SiO2 with the values of the other parameters will be determined. It will be shown that the simplest model with the smooth boundary is the most convenient with the experimental data. Copyright © 1999 John Wiley & Sons, Ltd.