Responsive PMO materials have been synthesized through co-assembly of bridged diacetylenic silsesquioxane and surfactant. The spatially defined polydiacetylenic component, mesoporous network, and the covalent proximity of polydiacetylene to silica endow the PMO with mechanical robustness, reversible chromatic responses, improved thermal stability, and faster responses to chemical stimuli. This research also provides an efficient molecular design and assembly paradigm to fabricate a family of conjugated optoelectronic materials, creating novel platforms for sensors, actuators, and other device applications.