The initial stages of wet thermal oxidation of Si(100)−(2×1) have been investigated by in situ ambient pressure x-ray photoemission spectroscopy, including chemical-state resolution via Si 2p core-level spectra. Real-time growth rates of silicon dioxide have been monitored at 100 mTorr of water vapor. This pressure is considerably higher than in any prior study using x-ray photoemission spectroscopy. Substrate temperatures have been varied between 250 and 500 °C. Above a temperature of ∼400 °C, two distinct regimes, a rapid and a quasisaturated one, are identified, and growth rates show a strong temperature dependence which cannot be explained by the conventional Deal-Grove model.