Nonstoichiometric GeO0.5[SiO2]0.5 and GeO0.5[SiO]0.5 germanosilicate glassy films are produced by the high-vacuum coevaporation of GeO2 and either SiO or SiO2 powders with deposition onto a cold fused silica substrate. Then the films are subjected to furnace or laser annealing (a XeCl laser, λ = 308 nm, pulse duration of 15 ns). The properties of the samples are studied by transmittance and reflectance spectroscopy, Raman spectroscopy, and photoluminescence spectroscopy. As shown by analysis of the Raman spectra, the GeO[SiO] film deposited at a substrate temperature of 100°C contains amorphous Ge clusters, whereas no signal from Ge–Ge bond vibrations is observed in the Raman spectra of the GeO[SiO2] film deposited at the same temperature. The optical absorption edge of the as-deposited GeO[SiO2] film corresponds to ~400 nm; at the same time, in the GeO[SiO] film, absorption is observed right up to the near-infrared region, which is apparently due to absorption in Ge clusters. Annealing induces a shift of the absorption edge to longer wavelengths. After annealing of the GeO[SiO2] film at 450°C, amorphous germanium clusters are detected in the film, and after annealing at 550°C as well as after pulsed laser annealing, germanium nanocrystals are detected. The crystallization of amorphous Ge nanoclusters in the GeO[SiO] film requires annealing at a temperature of 680°C. In this case, the size of Ge nanoclusters in this film are smaller than that in the GeO[SiO2] film. It is not possible to crystallize Ge clusters in the GeO[SiO] film. It seems obvious that the smaller the semiconductor nanoclusters in an insulating matrix, the more difficult it is to crystallize them. In the low-temperature photoluminescence spectra of the annealed films, signals caused by either defects or Ge clusters are detected.