The atomic structure and electron spectrum of a-SiOx:H films deposited on silicon and glass substrates by the plasma enhanced chemical vapor deposition method are considered in this paper. The film stoichiometric parameter «x» varied in the range from 0.57 to 2 depending on the oxygen supply to the reactor conditions. The film structures and the electronic structure peculiarities characterization, depending on the parameter «x» value, were carried out using a set of structural and optical techniques, as well as the ab initio quantum-chemical simulation for the model SiOx structure. It was established that the studied SiOx:H films mainly consist of silicon suboxide SiOy with SiO2 and amorphous Si clusters. Based on the spatial chemical composition fluctuations, the electron and hole potential fluctuations model for SiOx is proposed. The obtained results will allow a more accurate charge transport modeling in a-SiOx:H films, which is important for creating nonvolatile memory and memristor elements on the base of SiOx.