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A new mononuclear vanadium peroxido complex [VO(O2)(phen)(quin)]·H2O (1) exhibiting an unprecedented isomerism of its ligands was isolated from a two-component water-acetonitrile solvent system. DFT computations aimed at inspecting the stability of all possible isomers of complexes [VO(O2)(L1)(L2)], where L1 and L2 are NN+ON, OO+ON, NN+OO, and ON+ON donor atom set ligands, suggested that every complex characterized so far was the one preferred thermodynamically. However, the particular case of complex [VO(O2)(phen)(quin)]