A new series of oxovanadium(V) 1,2-diolate compounds have been prepared, characterized, and structurally investigated. The reactions of oxovanadium trialkoxides with trans-1,2-cyclohexanediol,(+/-)-2,3-butanediol,2R,3R-butanediol, and ethylene glycol produced yellow solid materials. These materials contain two diols for each vanadium presumably in a dimeric arrangement. Solution-state V-51 NMR spectroscopy reveals the presence of complex association and ligand exchange equilibria, necessitating structural characterizations in the solid state. Since single-crystal X-ray diffraction analysis studies were limited as a result of disorder, the materials were characterized by solid-state V-51 and C-13 NMR spectroscopy. Field-dependent line-shape analysis of static and MAS V-51 solid-state NMR spectra obtained on a series of characterized compounds provide benchmark isotropic and anisotropic chemical shift data. These parameters can be correlated to distinct local vanadium coordination environments. On the basis of this correlation, possible structural models for the new oxovanadium 1,2-diolate derivatives were obtained and confirmed by other spectroscopic methods. Changes in coordination about the vanadium atom have been observed when trans-1,2-cyclohexanediol,(+/-)-2,3-butanediol, or 2R,3R-butanediol is replaced by ethylene glycol. It appears that the molecular geometry about the vanadium atom is very sensitive to minor perturbations in the ligand.