The paper reviews the non-destructive depth profiling of the composition and the chemical structure of high-κ/Si and high-κ/Ge using angle-resolved photoelectron spectroscopy. We have investigated the influence of the post deposition annealing on compositional depth profiles and chemical structures of high-κ/semiconductor and the influence of Si-cap layer on chemical structures of HfO2/Si-cap/strained Ge/SiGe/Si interfaces by angle-resolved X-ray photoelectron spectroscopy. Analyses of Si 2s spectra show that the silicate was formed at high-κ layer / Si interface during the deposition and that the reactivity between ScOx or CeOx and Si substrate is lower than that between LaOx and Si substrate. Analyses of Ge 2p, Si 1s and Hf 3d spectra show that the strained-Ge layer was oxidized during the deposition of HfO2 in the case of 1 nm Si cap layer and that strained-Ge layer was not oxidized in the case of 3nm and 5nm Si cap layer. A critical Si thickness also extracted.