Using the method of photoelectron spectroscopy, an in situ study in ultrahigh vacuum of the electronic structure of a clean surface of tungsten oxidized at an oxygen pressure of 1 Torr and temperature of 1000 K was carried out. The spectra of photoemission from the valence band and core levels O 1s, O 2s, W 4f under synchrotron excitation in the photon energy range 80 600 eV are studied. It was found that a semiconductor film of tungsten oxide is formed, which contains various tungsten oxides with an oxidation state of 6+ to 4+. On the surface, mainly tungsten oxides with an oxidation state of 6+ are formed, the proportion of which gradually decreases with distance from the surface with an increase in tungsten oxides with an oxidation state of 4+.