A green V(Ⅲ) compound, imidazolium hexafluorovanadium(Ⅲ), [C3H5N2)]3[VF6] (1),has been prepared and characterized.The geometric structure and electronic structure, together with charge-transfer, optical and bonding properties thoroughly investigated by X-ray crystallography,density functional theory level (DFT) and time-dependent density functional theory level (TDDFT) calculations.The low-energy charge-transfer bands responsible for its green color may be theoretically assigned to F(2p)→V(4p) ligand-to-metal charge transfer transition (LMCT) in nature.While the ligand-field charge-transfer bands (d→d bands) occur at a lower energy region, which is too weak and will be obscured by these quite intense LMCT bands in the optical spectrum.The partial density of states (PDOS) analysis clearly shows that the nature of metal-ligand interactions in [VF6]3-is mainly ionic.