We report an evaporation-induced self-assembly procedure to prepare poly(bridged silsesquioxane) thin-film and particulate mesophases that incorporate organic moieties (1-3) into periodic, mesostructured frameworks as molecularly dispersed bridging ligands. Capacitance-voltage measurements along with a variety of structural characterization procedures were performed to begin to elucidate structure-property relationships of this new class of surfactant-templated mesophases. We observed a consistent trend of increasing modulus and hardness and decreasing dielectric constant with substitution of the bridged silsesquioxane (drop Si-(CH2)-Si drop) for siloxane (drop Si-O-Si drop) in the framework. This preliminary evidence suggests that the introduction of integral organic groups into the frameworks of mesoporous materials can result in synergistic properties, promising an unprecedented ability to tune properties and function.