A method for disproportionation of an oligohydridosiloxane to produce a polysilsesquioxane compound and an organohydridosilane compound when contacted with a basic catalyst. The basic catalyst can be a tetraalkylammonium hydroxide, an alkali metal hydroxide, and an alkali earth hydroxide. These basic catalysts are generally dissolved in an organic solvent for delivery. The hydroxide catalysts are attractive because many readily decompose by heating above 150.degree. C., thus being easily removed from the final materials. The oligohydridosiloxane is contacted with the basic catalyst under conditions effective to catalytically convert the oligohydridosiloxane into a polysilsesquioxane compound and an organohydridosilane compound. The reaction can occur in either an inert or oxidative atmosphere and can occur without heating, at room temperature. Both polysilsesquioxane foams and gels of the formula (RSiO.sub.1.5).sub.n can be produced.