We have discovered new Meerwein's reagent-catalyzed sol-gel polycondensations, which provide highly condensed silica Q(4) and biphenylylene silica T-3 as amorphous gels with marginal silanols starting from TEOS and 4,4'-bis(triethoxysilyl)biphenyl (BTEBph), respectively. We propose a plausible pathway for this protocol with possible silyloxonium intermediates.