The central V(V) atom in the title mononuclear oxovanadium complex, [VO(C(23)H(20)N(2)O(4))(CH(3)OH)]·H(2)O, has a distorted octahedral coordination. Two N atoms and two O atoms of the Schiff base define the base of the bipyramid and two O atoms are in the apical positions, one from vanadyl and the second from methanol. Density functional theory (DFT) calculations were performed for the title complex and its ligand to compare their geometry in the solid and gas phases. Additional analyses were made of the changes in the geometry of the ligand during complex formation. The HOMA (harmonic oscillator model of aromaticity) descriptor of π-electron delocalization was calculated to estimate the aromaticity of the benzene rings in the title complex and its ligand.