A new family of trinuclear homo- and heterometal complexes with a triangular [V(V)O-MO-V(V)O] (M = V(IV), 1 and 2; Re(V), 3] all-oxido-metal core have been synthesized following a single-pot protocol using compartmental Schiff-base ligands, N,N'-bis(3-hydroxysalicylidene)-diiminoalkanes/arene (H4L1-H4L3). The upper compartment of these ligancis with N2O2 donor combination (Salen-type) contains either a V(IV) or a Re(V) center, while the lower compartment with O-4 donor set accommodates two V(V) centers, stabilized by a terminal and a couple of bridging methoxido ligands. The compounds have been characterized by single-crystal X-ray diffraction analyses, which reveal octahedral geometry for all three metal centers in 1-3. Compound 1 crystallizes in a monoclinic space group P2(1)/c, while both 2 and 3 have more symmetric structures with orthorhombic space group Pnma that renders the vanadium(V) centers in these compounds exactly identical. In DMF solution, compound 1 displays an 8-line EPR at room temperature with < g > and < A > values of 1.972 and 86.61 x 10(-4) cm(-1), respectively. High-resolution X-ray photoelectron spectrum (XPS) of this compound shows a couple of bands at 515.14 and 522.14 eV due to vanadium 2p(3/2) and 2p(1/2) electrons in the oxidation states +5 and +4, respectively. All of these, together with bond valence sum (BVS) calculation, confirm the trapped-valence nature of mixed-oxidation in compounds 1 and 2. Electrochemically, compound 1 undergoes two one-electron oxidations at E-1/2 = 0.52 and 0.83 V vs Ag/AgCl reference. While the former is due to a metal-based V(IV/V) oxidation, the latter one at higher potential is most likely due to a ligand-based process involving one of the catecholate centers. A larger cavity size in the upper compartment of the ligand H4L3 is spacious enough to accommodate Re(V) with larger size to generate a rare type of all-oxido heterotrimetallic compound (3) as established by X-ray crystallography.