Amines are used as pH control agents to form macroporous silica gels utilizing macroscopic phase separation of acid-catalyzed tetraethoxysilane water binary mixture. The wide pK(a) variety of amines from basic to acidic regions is suitable to buffer the solution at neutral pH range, at which the phase separation becomes prominent. This method allows monolithic silica gels and glasses to be prepared reproducibly from alkoxide-based solutions with minimal use of pH control agents.