Heterobimetallic compounds [L'OVV(mu-O)-((ML)-L-III](n) (n = 1, M = Mn, 1-5; n =2, M = Fe, 6 and 7) containing a discrete unsupported V-V-O-M-III bridge have been synthesized through a targeted synthesis route. In the V-O-Mn-type complexes, the vanadium(V) centers have a square-pyramidal geometry, completed by a dithiocarbazate-based tridentate Schiff-base ligand (H2L'), while the manganese(III) centers have either a square-pyramidal (1 and 3) or an octahedral (2 and 5) geometry, made up of a Salen-type tetradentate ligand (H2L) as established by X-ray diffraction analysis. The V-O-Mn bridge angle in these compounds varies systematically from 155.3 degrees to 128.1 degrees in going from 1 to 5 while the corresponding dihedral angle between the basal planes around the metal centers changes from 86.82 degrees to 20.92 degrees, respectively. The V-O-Fe-type complexes (6 and 7) are tetranuclear, in which the two dinuclear V(mu-O)Fe units are connected together by apical iron(III) aryl oxide interactions, forming a dimeric structure with a pair of Fe-O-Fe bridges. The X-ray data also confirm the V=O -> M canonical form to contribute predominantly on the overall V-O-M bridge structure. The molecules in solution also retain their heterobinuclear composition, as established by electrospray ionization mass spectrometry and V-51 NMR spectroscopy. Electrochemically, these complexes are quite interesting; the manganese(III) complexes (1-5) display three successive reductions (processes I III), each with a monoelectron stoichiometry. Process I is due to a Mn-III/Mn-II reduction (E-1/2 ranges between -0.32 and -0.05 V), process 11 is a ligand-based reduction, and process III (E-1/2 = similar to 1.80 V) owes its origin to a (VO)-O-V/(VO)-O-IV reduction; all potentials are versus Ag/AgCl. The iron(III) compounds (6 and 7), on the other hand, show at least four irreversible processes, appearing at E-pc = -0.20, -1.0, -1.58, and -1.68 V in compound 6 (processes IV-VII), together with a reversible process (process VIII) at E-1/2 = -1.80 V (Delta E-P = 80 mV). While the first two of these are due to Fe-III/Fe-II reductions at the two iron(III) centers of these tetranuclear cores, the reversible reduction at a more negative potential (ca. -1.80 V) is due to a (VO)-O-V/(VO)-O-IV-based electron transfer.