Solid state H-1, Si-29 and (31)p MAS NMR have been used to investigate the microstructure of phosphosilicate gels prepared by a modified sol-gel method involving hydrolysis of silicon precursors in a solely aqueous environment at 50degreesC. Gels with molar compositions 5, 10, 20 and 30 mol% P2O5 in P2O5-SiO2 were studied. After drying to 400degreesC the gels have very similar structure, formed by a siloxane framework containing silanol groups and trapped molecules of orthophosphoric acid together with a very small amount, of pyrophosphoric acid. Unlike the gel samples previously synthesized by the hydrolysis of the silicon precursor in alcoholic solution at room temperature, the co-polymerization of phosphorus and silicon is much reduced. Although co-polymerization increases with phosphorus content, it still represents less than 50% of the phosphorus in the 30 mol% P2O5 gel. Furthermore there is no evidence for six-coordinated silicon in the glassy matrix. (C) 2004 Published by Elsevier B.V.