Binuclear pivalate complexes of 3d transition metals (manganese, iron, cobalt, and nickel) with the same ligand environment and a lantern structure have been studied by X-ray photoelectron spectroscopy. The M2p, M3s, C1s, O1s, and N1s X-ray photoelectron spectra have been examined. A redistribution of elec- tron density in the OCO group has been revealed. It has been shown that the theory fits the experimental data on the energy separation between the high- and low-spin components in the M3s spectra and between the spin doublet components in the M2p spectra. It has been demonstrated that the iron, cobalt, and nickel com- plexes are paramagnetic at room temperature, whereas the manganese complex exhibits antiferromagnetic properties. There is a correlation between the size of the 3d subshell of the transition metal atom and the M- O and M-N bond lengths. © Pleiades Publishing, Ltd., 2012.