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[en] The electronic structure of the Co3+ cations in perovskite cobaltites Sc1 –yCo1 –xFexO3 – (3/2)y (x = 0, 0.05; y = 0.1) and BiCoO3 has been studied by X-ray photoelectron spectroscopy. Our measurements have been made in the energy range 0–1250 eV, which has allowed us to determine the binding energies and to characterize the structure of the spectra for both valence and inner electrons of the cobalt cations in detail. Based on the results obtained, we have analyzed the valence and spin states of the cobalt cations and the structure of their local crystalline environment in the oxides under consideration. The influence of the surface etching of cobaltite samples on the electronic state of cobalt has been studied.