Oxygen bonding in La-silicate film with compositional gradient has been characterized by x-ray photoelectron spectroscopy. Based on an analytical model of bridging and nonbridging oxygen, the O 1s spectra arising from La-silicate layer have been deconvoluted with compositionally dependent parameters. For a composition ratio of 1:1 for SiO2 and LaO1.5 on the surface of the La-silicate layer, negative binding energy shifts of 0.35 and 0.10 eV for bridging and nonbridging oxygen, respectively, have been found to well interpret the angle-resolved spectra. The method has also been applied to characterize the temperature dependence of interface reactions at La 2O3/Si with in situ processed Pt electrode. SiO 4 molecules combined with bridging and nonbridging oxygen atoms have been found to form by high temperature annealing. The thickness of the silicate layer of 0.4 nm at as-deposited state has been found grow up to 2.8 nm after 500 °C annealing. From rough estimation, it has been revealed that 10% of the newly created bridging oxygen atoms by annealing are incorporated into SiO 4 network which contain also nonbridging oxygen atoms.