The solution chemistry of vanadium(V) species in an aqueous alcoholic silicate solution was studied by V-51 NMR spectroscopy. It was found that under conditions of low water, vanadium silicate species, containing V-O-Si Linkages, formed immediately and remained at approximately steady-state concentrations during most of the reaction. Al high concentrations of water, the oxovanadium triisopropoxide reacts quickly through hydrolysis and self-condensation to form vanadate species. The observation of these different species in solution provides a detailed, molecular-level interpretation of the factors that influence the formation of homogeneous, multicomponent vanadia-silica glasses made through the sol-gel process.