This brief review deals with the development of a general protocol for the synthesis of μ-oxido divanadium(V) compounds [LOV V -(μ-O)-V V O(Salen)] (L=L 1 –L 5 ) (1–5) incorporating coordination asymmetry. One of the vanadium centers in these compounds has an octahedral environment, completed by tetradentate Salen ligand, while the other center has a square pyramidal geometry, made up of tridentate biprotic Schiff-base ligands (H 2 L 1–5 ) with ONO (1–3) and ONS (4, 5) type donor combinations. Single crystal X-ray diffraction, ESI-MS, and multi-nuclear NMR ( 1 H and 51 V) spectroscopy have been used extensively for the characterization of these compounds. The V 2 O 3 core in these compounds, save 3, has a rare type of twist-angular structure. The V(1)⋯V(2) separations (3.7921(7)–3.3084(6)Å) are by far the largest in these compounds compared to their peers containing a V 2 O 3 core. The molecules retain their unsymmetrical binuclear structures also in solution as established by NMR spectroscopy. The mixed-oxidation compound (ImH)[L 4 OV IV -(μ-O)-V V OL 5 ] 7 containing two dissimilar ligands has a V 2 O 3 core with a syn-angular structure and exhibits crystallographically imposed mirror symmetry due to static disorder. In solution of donor solvents, this angular core structure changes into a linear one (anti-linear) by accepting solvents in to the vacant coordination site of the metal centers. Finally, the protocol for the synthesis of heterobimetallic compounds with vanadium(V) and Re(VII) combination flanked by a single μ-oxido bridge has been developed in which the precursor complexes [V IV OL 6,7 ] (H 2 L 6,7 are Salen type of ligands) are allowed to oxidize aerially in the presence of added perrhenate anion. The oxidized [V V OL 6,7 ] + species hold the ReO 4 − anion in the vacant coordination site of the metal ion, trans to the terminal oxido group, thus generating the V V –O–Re VII moiety in the heterobimetallic compounds (9 and 10). Both X-ray crystallography and 1 H NMR spectroscopy have been used to establish the identities of these compounds. In compound 9, the Re(1)–O(11)–V(1) bridge angle is barely linear (170.2(3)°) with a Re⋯V separation of 3.9647(9)Å. The redox behavior of 9 and 10 are quite interesting, each undergoing two reductions both in the positive potential range at E 1/2 =0.59 and 0.16V vs. Ag/AgCl reference and have single-electron stoichiometry, confirmed by constant potential coulometry.