Abstract The interactions of germanium, boron, phosphorus and fluorine dopants with the defect sites of vitreous silica were studied by the Raman spectroscopy method. The scattering cross sections of Raman lines associated with SiOGe, SiOB, P=0 and SiF structural groups were found, which made it possible to determine directly from spectra the absolute values of concentrations of the dopants listed. The incorporation of dopants into silica was shown to occur mainly over the defect sites of a silica network. The defects play the most significant role when germanium is incorporated, which is explained, apparently, by the structural similarity of silicate and germanate glasses. The generation of chemical groups of the GeO 2 phase (GeOGe) in place of defect sites was noticed. A similar effect was not observed for boron and phosphorus groups. The nature of defect sites responsible for 606 and 490 cm −1 Raman lines is discussed.