Breakdown voltage, static current-voltage, spectroscopic ellipsometry (SE), electrolyte electroreflectance (EER) and high resolution transmission electron microscopic (HRTEM) studies of thermally grown thin films of SiO2 on silicon (800°C - dry) are reported here. The investigation of the electrical properties of these films lead us to suggest the criteria for determining the breakdown voltage of these 20nm thick SiO2 films. The Fowler-Nordheim tunneling contribution to current conduction mechanisms in SiO2 has been considered in evaluating these criteria. SE, EER & HRTEM studies have been performed on SiO2 films of thicknesses in the range of 1–20 nm. These studies lead us to determine the thickness of the non-stoichiometric silicon-rich oxide existing at the Si-SiO2 interface. EER studies show that the relative surface state densities for different film thicknesses can be determined. The role of the transition region in determining the dielectric strength of thin SiO2 films is discussed.