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Abstract Detailed electrical and photoemission studies were carried out to probe the chemical nature of the insulating ground state of VO₂, whose properties have been an issue for accurate prediction by common theoretical probes. The effects of a systematic modulation of oxygen over-stoichiometry of VO₂from 1.86 to 2.44 on the band structure and insulator–metal transitions are presented for the first time. Results offer a different perspective on the temperature- and doping-induced IMT process. They suggest that charge fluctuation in the metallic phase of intrinsic VO₂results in the formation of e⁻and h⁺pairs that lead to delocalized polaronic V³⁺and V⁵⁺cation states. The metal-to-insulator transition is linked to the cooperative effects of changes in the V–O bond length, localization of V³⁺electrons at V⁵⁺sites, which results in the formation of V⁴⁺–V⁴⁺dimers, and removal of$$\pi^{*}$$ ${\pi }^{\ast }$screening electrons. It is shown that the nature of phase transitions is linked to the lattice V³⁺/V⁵⁺concentrations of stoichiometric VO₂and that electronic transitions are regulated by the interplay between charge fluctuation, charge redistribution, and structural transition.