[en] The electronic and molecular structure of vanadium isopolyanions and heteropolyanions was studied with NMR of ⁵¹V since vanadium nucleus is sensitive to electronic environment. Chemical shifts of NMR lines of ⁵¹V are measured. The NMR chemical shifts of ⁵¹V enable to trace the effect of oxygen atoms in the neighbourhood of vanadium in its isopolyanions and heteropolyaniuns depending on the metal in the coordination sphere. Linear correlation was observed between the NMR chemical shifts of ⁵¹V and < g > factors of the reduced forms with vanadium in the oxidation state +4