The hybridization of vanadium ions and oxygen ions is considered for four vanadium oxides included in the Magneli series: VO, V2O3, VO2, V2O5. Based on the data on hybridization, the details of the structure of the crystal lattice of these oxides are analyzed. For each oxide, the role of electrons not participating in the stabilization of the crystal frame in the process of the semiconductor-metal phase transition was revealed. The complex Mott-Peierls character of the phase transitions in all the listed strongly correlated compounds has been established. It is shown that as the degree of oxidation of the V atom increases, the numerical value of the metallic conductivity of the high-temperature phase naturally decreases and, simultaneously, the temperature of the phase transition from the semiconductor to the metallic state increases. Keywords: phase transitions, Magneli series, electron correlations, hybridization of atomic orbitals.