The phase separation and gel formation behavior in an alkoxy-derived silica sol-gel system containing C16EO15 has been investigated. Various gel morphologies similar to other sol-gel systems containing organic additives were obtained by changing the preparation conditions. Micrometer-range interconnected porous gels were obtained by freezing transitional structures of phase sepa- ration in the sol-gel process. The dependence of the resulting gel morphology on several important reaction parameters such as the starting composition, reaction temperature and acid catalyst concentration was studied in detail. The experimental results indicate that the gel morphology is mainly determined by the time relation between the onset of phase separation and gel formation. The phase separation and gel formation behavior in an alkoxy-derived silica sol-gel system containing C16EO15 has been investigated. Various gel morphologies similar to other sol-gel systems containing organic additives were obtained by changing the preparation conditions. Micrometer-range interconnected porous gels were obtained by freezing transitional structures of phase separations in the sol-gel process. The dependence of the resulting gel morphology on several important reaction parameters such as the starting composition, reaction temperature and acid catalyst concentration was studied in detail. indicate that the gel morphology is primarily determined by the time relation between the onset of phase separation and gel formation.