Hydrolysis and condensation of trialkoxysilanes, HSi(OMe)3 and HSi(OEt)3, has been used to prepare polyhydridosilsesquioxaes for dielectric applications. In this study we examined the ability of trimethoxysilane (TMS) and triethoxysilane (TES) to undergo sol-gel polymerization to afford gels. Sol-gel polymerization experiments were conducted under acidic (HCl), basic (NaOH), and neutral conditions in methanol or ethanol. Gels prepared with basic catalysts were exothermic with the evolution of hydrogen gas. Gel times are compared with silica gels prepared from tetramethoxysilane (TMOS) and tetraethoxysilane (TEOS). Gels were worked up under aqueous conditions to afford xerogels. Surface area analyses by nitrogen sorption porosimetery revealed that the materials were mostly mesoporous materials with surface areas in the hundreds of square meters per gram. Solid state 29Si CP MAS NMR was used to determine the amount of hydrido group remaining in the xerogels. Gels prepared under acidic conditions were essentially polysilsesquioxanes with very little loss of hydride functionalities. In gels prepared under basic conditions the hydride groups were completely gone leaving silica gels. Gels prepared with neutral water lost approximately 66% of the hydride groups.