Cage octasilsesquioxane with various substituents were obtained by the condensation reaction of various all-cis cyclic tetrasiloxanetetraol (R-T 4 -tetraol, R=phenyl, p-tolyl, i-butyl, naphthyl) with benzyltrimethylammonium hydroxide or tetrabutylammonium fluoride as a catalyst. Co-condensation of phenyl-T 4 -tetraol with phenyl-d 5 -T 4 -tetraol or with p-tolyl-T 4 -tetraol were found to proceed through reshuffling process evidenced by scrambling of the substituents. Pure octa(4-bromo-substituted phenyl)octasilsesquioxane was synthesized for the first time from tetra(4-bromo-substituted phenyl)tetrasiloxanetetraol sodium salt.