The electronic structure of cobalt complexes with bi-, tri-, and tetradentate ligands and the mutual influence of ligands in them have been studied by X-ray photoelectron spectroscopy. The Co2p, N1s, and O1s photoelectron spectra have been studied. Unlike low-spin Co(III) complexes, the high-spin Co(II) compound exhibits a strong satellite line in the Co2p spectrum. For the high-spin Co(II) compound having unpaired 3d electrons, the Co2p1/2-Co2p3/2 spin-orbit splitting is larger than that in the low-spin Co(III) complexes. All cobalt complexes under consideration contain strongly bound dioxygen, which can be considered an inherent structural unit.