In this work, the structural transformations of a suboxide vacuum-deposited film of SiO_1.3 composition annealed in an inert atmosphere in a wide temperature range of 100 °C–1100 °C were characterized by the reflection-transmission spectroscopy technique. The experimental spectroscopic data were used to obtain the spectra of the absorption coefficient α(hν) in the absorption edge region of the film. Based on their processing, the dependences of Urbach energy E_U and optical (Tauc) bandgap E_o on the annealing temperature were obtained. An assessment of the electronic band gap (mobility gap) E_g was also carried out. Analysis of these dependences allowed us to trace dynamics of thermally stimulated disproportionation of the suboxide film and the features of the formation of nanocomposites consisting of amorphous and/or crystalline silicon nanoparticles in an oxide matrix.