Phase separation which occurs in parallel to the hydrolysis and gelation of alkoxysilane solution containing poly(sodium styrenesulfonate) (NaPSS) has been investigated. Depending on the reaction conditions, gel morphologies such as isolated pores, particle aggregates, and interconnected continuous pores from 0.1 to 100-mu-m long have been observed. Time-resolved light scattering of gelling solution suggested the occurrence of spinodal phase separation through the polymerization of silica and the subsequent freezing of the developing structure by sol-gel transition. The effects of reaction parameters on the periodic size are explained mainly in terms of their influence on the "chemical cooling" rate which is determined by the polymerization rate of silica and the solubility of NaPSS in the reacting solution.