The electronic structures of vanadium centers coordinated by three dithiolene ligands have been elucidated by using a host of physical methods: X-ray crystallography, cyclic voltammetry, electronic absorption, electron paramagnetic resonance (EPR), and X-ray absorption spectroscopies, augmented by density functional theoretical (DFT) calculations. The consensus electronic structure derived from this approach is a V(IV) central ion for the neutral, monoanionic, and dianionic members of this electron transfer series, where the tris(dithiolene) ligand units are (L-3)(4-), (L-3)(5-center dot), and (L-3)(6-), respectively. The trigonal prismatic monoanions, [V-IV(L-3(5-center dot))](1-) (S=0), are defined as singlet diradicals where the crystallographically observed dithiolene fold results from strong antiferromagnetic coupling between the metal- and ligand-based magnetic orbitals. These results are contrasted with the corresponding tris-(dioxolene)vanadium electron transfer series toward establishing the factors that govern the molecular trigonal prismatic or octahedral geometries in systems with three redox noninnocent ligands.