High resolution X-ray photoelectron spectroscopy (XPS) is used to investigate the spectra of nanolayered films. Amorphous gallium oxide (Ga2O3)-silicon dioxide (SiO2) nanolayered thin films are grown using ultrahigh vacuum radio frequency (rf) magnetron sputtering on sapphire substrates at room temperature. Films are layered with 15-angstrom Ga2O3 oxide and 75-angstrom SiO2 for a total of 10 layers. Referring to atomic core levels, atomic contribution to valence band density of states is experimentally nominated. This analytical technique has particular applicability to the evaluation of the density of states with atomic contributions.