Geometric and electronic environments of vanadium have been addressed by V-51 magic angle spinning NMR spectroscopy of six-coordinated polyoxometalate solids. (C4H9)(4)N+ and mixed Na+/Cs+ salts of the Lindqvist-type mono- and divanadium-substituted oxotungstates, [VW5O19](3-) and [V2W4O19](4-), have been prepared as microcrystalline and crystalline solids. The solid-state NMR spectra reflect the details of the local environment of the vanadium site in these hexametalate solids via the anisotropic quadrupolar and chemical shielding interactions. Remarkably, these V-51 fine structure constants in the solid state are dictated by the nature and geometry of the countercations. Electrostatic calculations of the electric field gradients at the vanadium atoms have been performed. Experimental trends are well reproduced with the simple electrostatic model, and explain the sensitivity of the anisotropic NMR parameters to the changes in the cationic environment at the vanadium site.