•Nanometer silica films were synthesized by different methods and processed in hydrogen plasma.•Low-temperature luminescence excited by synchrotron radiation in VUV region was studied.•The conversion of hydrogen passivated emission centers was observed.•The luminescence of quantum dots was manifested in the emission spectra. Optically active defects in modified silicon oxide films on a silicon substrate have been studied by low-temperature photoluminescence (PL) spectroscopy using excitation by synchrotron radiation in the vacuum ultraviolet region. Films of dry thermal silicon oxide obtained by treatment of stoichiometric SiO2 in hydrogen plasma, films of wet thermal silicon oxide, and films with low dielectric constant (so called "low-k" dielectrics) have been studied. Investigations of various type SiO2 films detect the PL centers, which can be conditionally divided into two groups. The first group includes intrinsic point defects, the different variants of oxygen-deficient centers (ODCs). The second group contains centers like the spatially confined excitons in silicon quantum dots (SiQDs). It is shown that SiQDs differ in spectral characteristics, are formed in different ways, due to the transformation and clustering of point defects such as E'-centers, ODC(I) and ODC(II). In this case, the size and spectral properties of quantum dots depend on the mechanism of their formation. Schemes for the conversion of these defects are proposed. It was found that for wet films and nonstoichiometric SiOx films treated in hydrogen plasma, "metastable" centers ODC(I) and ODC(II) arise only under the action of synchrotron radiation in the region of interband or exciton absorption and then they decay because of radiative relaxation. The absence of stable ODC centers in these films is due to their clustering and the formation of SiQDs. In "low-k" mesoporous films, on the contrary, silicon quantum dots SiQDs are not formed, but ODC(I) and ODC(II) centers are clearly manifested. A scheme of electronic transitions upon indirect excitation of silicon quantum dots through exciton states of the SiO2 matrix is considered. The presented results demonstrate the possibility of controlling the optical properties of silicon thin-film structures by creating in them both oxygen-deficient point defects and quantum dots of various sizes.