The degradation behavior of the sulfur-treated InP surface at relatively low temperature has been investigated with x-ray photoelectron and photoluminescence (PL) spectroscopy. The results showed that the treated surfaces were oxidized to In2O3, InPO3, and InPO4 at 250 °C and in a vacuum of 10−3 Torr for 20 min. As the holding time for S-treated InP under a vacuum of 10−3 Torr increased, the PL peak caused by the band edge transition decreased without the formation of oxides. It was therefore suggested that the decrease of the PL intensity for S-treated InP is only related to the generation of phosphorous vacancies at the surface, not to oxide formation. The usefulness of a thin S overlayer on III–V semiconductors was also discussed.