Variable angle spectroscopic ellipsometry of very thin T2O5 layers on Si and the previously published appropriate algorithm for data interpretation have been successfully applied in terms of accurate characterization of very thin T2O5/Si systems. The simulation procedure following a simple three and four layered model was used assuming an existence of inhomogeneous interfacial layers. Quantitative determination of the thicknesses and composition identification were achieved, both for the top T2O5 layer and for an interfacial layer. The constituents in the interfacial layer and its depth profiles were recognized. (C) 2009 Elsevier B. V. All rights reserved.