This overview paper includes both published and original data of the current state of the field of V-51 NMR in solid-state chemistry. Advantages and shortcomings of different NMR techniques in their applications to vanadium are discussed on the examples of their application to various vanadia based systems (including individual highly crystalline compounds, solid solutions, glasses, catalysts). New correlations between local structure of vanadium atoms and NMR parameters allowing to discriminate at least seven different types of vanadium sites (tetrahedral sites of Q(0), Q(1) and Q(2) types; trigonal pyramids of 3 = 1 and 3 = 2 (V2O5 like) types; tetragonal pyramids of 4 = 1, 4 = 2 types) are proposed. It is demonstrated that competent combination of different NMR approaches permits now not only to describe different vanadium sites in highly crystalline and amorphous materials, but also to insight into the structural aspects of disorder in crystallinity as well as to reveal the behavior of different functional groups at elevated temperatures. The influence of low valence vanadium atoms on V-51 NMR spectra is also discussed.