Reaction of the p-hydroquinone derivative H2Na4bicah·4H2O with either VIVOSO4·3H2O and NaVVO3 in equivalent quantities or with NaVVO3 yields the tetranuclear VIVO2+ macrocycle–semiquinonate compound Na6{(VIVO)4(μ2-O)2[μ2-bicas·(−5)-N,O,O,O]2}·Na2SO4·20H2O (1·Na2SO4·20H2O) and the dinuclear cis-VVO2+–hydroquinone species Na4{(VVO2)2[μ2-bicah(−6)-N,O,O,O]}·11H2O (2·11H2O) respectively. Compounds 1·Na2SO4·20H2O and 2·11H2O were characterized by X-ray structure analysis and ab initio calculations.