Organic-inorganic hybrid monoliths with well-defined macropores and/or mesopores have been synthesized by a sol-gel process accompanied by polymerization-induced phase separation. Using aklyltrialkoxysilanes and alkylene-bridged alkoxysilanes, two different categories of organo-siloxane networks have been characterized in view of macroporoisity based on phase separation as well as mesoporosity based on supramolecular templating by surfactants. The alkyl-terminated polysiloxane network exhibited substantial surface hydrophobicity together with the mechanical flexibility. On the other hand, the alkylene-bridged network behaved much more similarly to those prepared from tetraalkoxysilanes with regard to surface hydrophilicity, mechanical rigidness and mesopore-forming ability. Supramolecular templating of mesopores embedded in the gel skeletons comprising well-defined macroporous network has proven to give wide variety of hierarchically designed macro-mesoporous organic-inorganic hybrid materials.