The results of an experimental study of X-ray photoelectron spectra and X-ray emission spectra of Kβl.3 samples of barium hexaferrites are presented. X-ray emission spectroscopy has shown that iron atoms are in a high-spin state. Theoretical calculations of Fe Kβ1.3 spectra and density of electronic states of BaFe12-xTixO19 (x = 1, 2.5) have been performed. It has been established by X-ray photoelectron spectroscopy that the ions of iron atoms have a valence of 2+ and 3+ as a result of the synthesis of compounds. The concentration of ions in the 2+ state reaches 40%.