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The effect of temperature on the electronic structure of Nb-doped SrTiO3 (100) surface is investigated by high-resoluyion synchrotron radiation photoemission spectroscopy. According to x-ray photoemission spectroscopy (XPS) re-sults, at an annealing temperature of less than 700?C, the adsorbed carbon and hydroxyl on STO surface could be removed, to expose the fresh intrinsic surface with a constant ratio of Ti/O. It is obvious that the STO would be doped by Ca+impurities of bulks and O vacancies in surface after annealing at 920?C for one hour.