The effect of the SiO2/Si interface on oxygen self-diffusion in SiO2 during thermal oxidation was investigated using oxygen isotopes. A Si18O2 layer was first grown in 18O2 and then the sample was reoxidized in 16O2 at 900 ~ 1100 °C. The O diffusion in SiO2 during the 16O2 oxidation was investigated by secondary ion mass spectrometry (SIMS) measurements. Near the SiO2/Si interface, a significant broadening of the 18O profile toward the newly grown Si16O2 was observed. This 18O diffusion became slower with oxidation time and hence with increasing distance between 18O diffusion region and the interface. This distance-dependent 18O self-diffusion was simulated taking into account the effect of SiO generated at the interface upon oxidation and diffusing into SiO2 to enhance O self-diffusion. The simulation fits the SIMS profiles and shows that the SiO diffusion is greatly retarded by the oxidation with O2 from the oxygen-containing atmosphere and that the O self-diffusion therefore becomes distance-dependent. In addition, near the SiO2 surface, 16O diffusion profiles develop with the 16O2 oxidation time from the surface into the initially grown Si18O2. The integrated surface 16O concentration increases with oxidation time and the SiO from the interface affects the O self-diffusion near the surface as well.