Isovalent mu-oxo divanadium(V) compounds [(LVO)-V-1(mu-O)VO(salen)] (1) and its bromo derivative [(LVO)-V-2(mu-O)VO(salen)]center dot CH3CN (2) (both H2L1 and H2L2 are tridentate dithiocarbazate-based ONS ligands) with ligands providing donor set and coordination number asymmetry in tandem have been synthesized for the first time; confirmations in favor of these unsymmetrical molecular structures have come from single-crystal X-ray diffraction analysis, as well as from NMR (both H-1 and V-51) spectroscopy.