Ultrathin SiO2 layers are of importance for the semiconductor industry. One of the techniques that can be used to determine the chemical composition and thickness of this type of layers is x-ray photoelectron spectroscopy (XPS). As shown by Seah and Spencer [Surf. Interface Anal. 33, 640 (2002)], it is not trivial to characterize this type of layer by means of XPS in a reliable way. We have investigated a series of ultrathin layers of SiO2 on Si (in the range from 0.3 to 3 nm) using XPS. The samples were also analyzed by means of transmission electron microscopy (TEM), Rutherford backscattering (RBS), and ellipsometry. The thickness of the SiO2 layers (d) was determined from the XPS results using three different approaches: the "standard" equation (Seah and Spencer) for d, an overlayer-substrate model calculation, and the QUASES-Tougaard [Surf. Interface Anal. 26, 249 (1998), QUASES-Tougaard: Software package for Quantitative Analysis of Surfaces by Electron Spectroscopy, version 4.4 (2000); http://www.quases.com] method. Good agreement was obtained between the results of XPS analyses using the "standard" equation, the overlayer-substrate model calculation, and RBS results. The QUASES-Tougaard results were approximately 62% above the other XPS results. The optical values for the thickness were always slightly higher than the thickness according to XPS or RBS. Using the model calculation, these (relatively small) deviations from the optical results could be explained as being a consequence of surface contaminations with hydrocarbons. For a thickness above 2.5 nm, the TEM results were in good agreement with the results obtained from the other techniques (apart from QUASES-Tougaard). Below 2.5 nm, significant deviations were found between RBS, XPS, and optical data on the one hand and TEM results on the other hand; the deviations became larger as the thickness of the SiO2 decreased. This effect may be related to interface states of oxygen, which have been investigated [D. A. Muller, T. Sorsch, S. Moccio, F. H. Baumann, K. Evans-Lutterodt, and G. Timp, Nature (London) 399, 758 (1999); D. A. Muller and J. B. Neaton, Structure and Energetics of the Interface Between Si and Amorphous SiO2 in Fundamental Aspects of Silicon Oxidation, edited by Y. J. Chabal (Springer, Berlin, 2001), pp. 219-246.] by means of high-resolution electron energy loss spectroscopy measurements of the O K edge in ultrathin gate oxides of SiO2. (C) 2004 American Vacuum Society.