Alkali-silica solutions containing varying amounts of silica and alkali ions have been prepared. Solids were obtained by interaction of these solutions with calcium hydroxide, calcium chloride or calcium sulphate. A Si-29 nuclear magnetic resonance study has been carried out on these products during the initial and final stages of the synthesis. Three major kinds of solids appear in the CaO-Na2O(K2O)-SiO2 phase diagram; a chain-like nanocrystalline solid, a plate-like amorphous solid, and a three-dimensional amorphous network solid. A relationship between the initial system (i.e., the initial solution) and the final system (i.e., the solid plus the residual solution) is established. The solid is found to have a higher degree of polymerization than the initial solution while the residual solution is mearly an alkali-silica solution without calcium ions.