The results of the studies of the point defect generation kinetics in the Si–SiO 2 system by means of electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) are presented. It has been established that the EPR and NMR signal intensities change non-monotonously with oxide film thickness and the maximum of the EPR and minimum of the NMR signals occur at the same oxidation time. This can be connected with the competition between the generation and transformation of the point defects, the formation of Si–O bonds and strained bonds rupture in the Si–SiO 2 system during the process of its formation. The defect structure of the Si–SiO 2 system depends on the point defects density in initial wafers. A possible mechanism to explain this interdependence has been discussed.