We have investigated chemical-state-resolved in-depth profiles of HfO 2 /SiO x and HfSiO/SiO x N y films using angular-dependent photoemission spectroscopy and Maximum-entropy method. Maximum-entropy method enables to reproduce the stack structure from angular-dependence of core-level spectra and it is utilized to determine atomic concentration of the interfacial layer. For the HfO 2 /SiO x film, it is elucidated that the Si + and Si 2+ sub-oxide components are located in the vicinity of Si substrate and Si 3+ is distributed around the interfacial layer. In addition, annealing-temperature dependence of in-depth profile for the HfSiO 2 /SiO x N y film have been demonstrated, which reveals that Si oxide components diffuse from the interfacial SiO x N y layer into the HfSiO layer during annealing.