Using X-ray photoelectron spectroscopy, we investigated the temperature dependence of the reaction rates at which oxidation of a hydrogen-terminated Si (Si–H) surface proceeds using H2O vapor. The rates of oxidation at temperatures lower than 250°C are not sensitive to the oxidation temperature or the number of impinging H2O molecules. This result indicates that the rate of oxidation of Si–H at lower temperatures are controlled by generation of activated Si–Si back bonds on Si substrates. On the other hand, the rates of oxidation at temperatures higher than 450°C are controlled by the rate at which hydrogen desorbs from the Si–H surface.