The electronic structure of the spin injecting La0.7Sr 0.3MnO3 (LSMO) thin film contacts was investigated using photoelectron spectroscopy. Clean LSMO surfaces were obtained by annealing at 450°C in vacuum, which additionally stabilized the oxygen content determined from the exchange splitting of the Mn(3s) x-ray photoelectron spectroscopy (XPS). The valence-band structure of the films showed features of metallic LSMO. The work-function measruements of clean, annealed films yield lower values due to oxygen depletion upon annealing.