ABSTRACTFormation of hierarchical macropores and mesopores in ethylene-bridged polysilsesquioxane sol-gel systems via concurrent sol-gel transition and phase separation induced by the incorporation of supramolecular templats has been investigated. A series of poly(ethylene-glycol)-poly(propyleneglycol)- poly(ethyleneglycol) triblock copolymers, EOPOEOs, have been employed as supramolecular templates, while 1,2-bis(trimethoxysilyl)ethane was used as a polysilsesquioxane source. Successful combination of templated mesopores and well-defined macropores due to phase-separation has been found in the system with EOPOEOs having 70 PO units and respective 20 EO units. Although similar macroporous morphology has been obtained for all the EOPOEOs with EO chain longer or shorter than 20 units, the optimum composition for the co-continuous macropores and that for templated mesopores deviated from each other, resulting in the failure of producing hierarchical macropores and mesopores.