This work presents a detailed study on the chemical composition and bond structures of CeO2/La2O3 stacked gate dielectrics based on x-ray photoelectron spectroscopy (XPS) measurements at different depths. The chemical bonding structures in the interfacial layers were revealed by Gaussian decompositions of Ce 3d, La 3d, Si 2s, and O 1s photoemission spectra at different depths. We found that La atoms can diffuse into the CeO2 layer and a cerium-lanthanum complex oxide was formed in between the CeO2 and La2O3 films. Ce3+ and Ce4+ states always coexist in the as-deposited CeO2 film. Quantitative analyses were also conducted. The amount of CeO2 phase decreases by about 8% as approaching the CeO2/La2O3 interface. In addition, as compared with the single layer La2O3 sample, the CeO2/La2O3 stack exhibits a larger extent of silicon oxidation at the La2O3/Si interface. For the CeO2/La2O3 gate stack, the out-diffused lanthanum atoms can promote the reduction of CeO2 which produce more atomic oxygen. This result confirms the significant improvement of electrical properties of CeO2/La2O3 gated devices as the excess oxygen would help to reduce the oxygen vacancies in the film and would suppress the formation of interfacial La-silicide also.