The structure of nonstoichiometric silicon oxide (SiOx) has been studied by the methods of highresolution X-ray photoelectron spectroscopy and fundamental optical-absorption spectroscopy. The conductivity of SiOx (x = 1.4 and 1.6) films has been measured in a wide range of electric fields and temperatures. Experimental data are described in terms of the proposed SiOx structure model based on the concept of fluctuating chemical composition leading to nanoscale fluctuations in the electric potential. The maximum amplitude of potential fluctuations amounts to 2.6 eV for electrons and 3.8 eV for holes. In the framework of this model, the observed conductivity of SiOx is described by the Shklovskii–Efros theory of percolation in inhomogeneous media. The characteristic spatial scale of potential fluctuations in SiOx films is about 3 nm. The electron-percolation energy in SiO1.4 and SiO1.6 films is estimated to be 0.5 and 0.8 eV, respectively.