La 0.67 Sr 0.33 MnO 3 (LSMO) films were prepared on SrTiO 3 single-crystal substrates by the pulsed laser deposition method. X-ray photoelectron spectra (XPS) were measured for the LSMO films as-prepared, annealed in oxygen and in vacuum, respectively. Multiple peaks fitting for Mn 2p 3/2 XPS spectra shows that Mn 2+ appears and the ratio of Mn 3+ /Mn 4+ increases on the surface of LSMO film annealed in vacuum comparing with the as-prepared film, though the saturation magnetization (M s ) changes little. Mn 6+ and Mn 7+ can be detected while Mn 4+ decreases much on the surface of LSMO film annealed in oxygen. The change of Mn 3+ /Mn 4+ results in the obviously reduce of M s . O1s spectra show the gradual changes of Mn-O, Sr-O and La-O. Analysis indicates that Mn 2+ forms at the surface defects of LSMO films. Annealing in vacuum hardly affects the magnetic property of LSMO films. But annealing in oxygen greatly changes the valence states of Mn, which weakens the magnetic property of LSMO films.