The electronic structure of the title VO(acac)(2) complex has been investigated using effective; core potential configuration interaction ab initio calculations, UV-photoelectron spectroscopy, and electronic spectroscopy. The metal-ligand bonding with the equatorial acac(-) ligands is dominated by a interactions involving the filled ligand orbitals and the empty orbitals of the d(1) vanadium(IV) ion. The oxovanadium interactions involve a larger metal-d participation thus resulting in a strong V-O bonding having partial triple-bond character. Additional three-orbital-four-electron stabilizing interactions involving the filled acac(-) MOs and the oxovanadium orbitals further reinforce both the axial and equatorial bonds. The unpaired metal-d electron is completely localized in the nonbonding d(x2-y2) orbital. The low ionization energy of the photoelectron spectrum has been fully assigned on the basis of combined Delta SCF and configuration interaction calculations. The same theoretical approach has, in addition, provided a good fitting of frequencies associated with "d-d" and charge transfer electronic transitions.