The materials chemistry of sol-gel-derived inorganic-organic molecular composites offers significant potential for molecular-level systems design. One focus in this arena is the chemical design and microstructural engineering of optically-active systems. We report the generation of rare-earth-doped inorganic-organic hybrids, based on a bridged polysilsesquioxane architecture. Derived from lanthanide precursors such as Erbium isopropoxide, which we co-condense with the requisite silsesquioxane monomer, these systems exhibit significant optical activity. In experiments on hybrids doped with Erbium, we conclusively demonstrate strong fluorescence at wavelengths in the vicinity of 1540 nm, from stimulation with 488 nm radiation. We discuss materials-driven impacts of the bridged-silsesquioxane architecture on system complexities arising from the solution sol-gel route which would affect fluorescence efficiencies and luminescence levels, such as hydroxyl impurities and clustering-effects.