The surface oxidation and HP desorption of powder CdS were studied by means of X-ray photoetectron spectroscopy (XPS), quadrupole mass spectrometry (QMS) and in-situ FTIR. The results show that with the changes of surface composition and the elongation of store time of CdS there are four types of H2O thermally desorbed at different temperatures. It has also been found that through high-temperature air treatment for a short time the oxidized surface layer of CdS can prevent O2 and H2O in air from further attacking the inner CdS molecules. The surface oxidation and HP desorption of powder CdS were studied by means of X-ray photoetectron spectroscopy (XPS), quadrupole mass spectrometry (QMS) and in-situ FTIR. The results show that with the changes of surface composition and the elongation of store time of CdS there are four types of H2O thermally desorbed at different temperatures. It has also been found that through high-temperature air treatment for a short time the oxidized surface layer of CdS can prevent O2 and H2O in air from further attacking the inner CdS molecules.