The non-stoichiometric germanosilicate films of two types GeOx[SiO](1-x) and GeOx [SiO2](1-x) were obtained by high-vacuum evaporation of GeO2 and either SiO or SiO2 powders and sputtering on a cold Si (001) substrate. The as-deposited and annealed (550 and 650 oC, 1 hour) samples were studied by IR spectrocopy, electron microscopy, Raman spectroscopy and photoluminescence (PL). From an analysis of Raman spectra, it was found that the as-deposited GeO[SiO2] film did not contain germanium clusters, and the as-deposited GeO[SiO] film contained amorphous germanium clusters; according to electron microscopy, it’s size was ~3 nm. According to IR spectroscopy, the films contained Si-O, Ge-O, and Si-O-Ge bonds. After annealing at 550 °C, amorphous germanium clusters were detected in both films, and after annealing at 650 °C, germanium nanocrystals were observed. A wide PL band with a maximum of 1050 nm was found in the as-deposited films at low temperatures. PL is probably due to defects, presumably oxygen vacancies and excess germanium atoms. Annealing causes a transformation of both film structure and PL spectra. In films containing germanium nanoclusters, PL is observed with a maximum of 1500–1600 nm. In this case, the PL signal from defects decreased. The temperature dependence of the intensity of the PL peaks was studied; it decreased with increasing temperature but remained at temperatures up to 200 K. The contribution to the PL from germanium nanocrystals formed during annealing is discussed.