The early oxidation stages of hydrogen-terminated single-crystalline Si(100) exposed to a diluted N 2 /N 2 O atmosphere at 850• C for different durations have been studied by XPS, following the evolution of the Si 2p signal. Evidence is given that the usual analysis, in terms of five pairs of peaks attributed to silicon in oxidation states from 0 to +4, does not account for the observed Si 2p signal. The spectrum is accurately reproduced only by assuming the existence of silicon in bonding configurations different from those usually assumed to occur at the Si/SiO 2 interface.