The mesostructured self-standing films with homogeneously distributed phenylene in the framework were synthesized using evaporation-induced coassembly of surfactant and 1,4-bis(triethoxysilyl)benzene. The addition of methyltriethoxysilane and dimethyldiethoxysilane to control the siloxane cross-linking network improved the flexibility and strength of films substantially. Thus obtained films also maintain their morphology with mesostructure even after calcination at 300 degrees C.