({ }^{51} \mathrm{~V}) static and magic-angle spinning (MAS) NMR spectra of crystalline monovalent metal metavanadates (\mathrm{LiVO}{3}, \alpha) - and (\beta) (\mathrm{NaVO}{3}, \mathrm{KVO}{3}, \mathrm{CsVO}{3}, \beta) - (\mathrm{AgVO}{3}), and (\mathrm{NH}{4} \mathrm{VO}{3}) and divalent metal metavanadates (M\left(\mathrm{VO}{3}\right){2}(M=\mathrm{Mg}, \mathrm{Ca}, \mathrm{Sr}, \mathrm{Ba}, \mathrm{Zn}, \mathrm{Pb})) have been measured in order to establish the relationships between the various NMR parameters, such as isotropic chemical shift, (\delta{\text {iso }}), chemical shift anisotropy, (|\Delta \delta|), the asymmetry parameter, (\boldsymbol{\eta}), and the crystallographic parameters. When the structural units are the same, in this case (\mathrm{VO}{4}) tetrahedra or (\mathrm{VO}{5}) trigonal bipyramids, the (\delta_{\text {iso }}) decrease almost linearly with decreasing average V-O bond length, independent of the polymerization degree and linkage mode of the (\mathrm{VO}{n}) polyhedra. (|\Delta \delta|) increases with the polymerization degree and the degree of the structural distortion of the (\mathrm{VO}{n}) polyhedron. It is found possible to predict the structural unit and the polymerization degree on the basis of the relation between (|\Delta \boldsymbol{\delta}|) and (\boldsymbol{\eta} . \quad \bigcirc 1994) Academic Press, Inc.