Silica gels with hierarchical macropores and mesopores have been prepared by inducing phase separation in the alkoxide-based sol-gel system with an addition of alkyltrimethylammonium salt. Narrowly distributed mesopores were observed in the heat-treated gel samples possibly as a result of supramolecular templating of silica oligomers in the reacting solution. The ionic attractive interaction and hydrophobicity of the attached alkyl group cooperatively determined the phase separation tendency. No indication of long-range order of the mesopores was obtained.