A room-temperature synthesis route for the fabrication of a new type of hybrid organic/inorganic mesostructured material based on titania instead of silica as the inorganic component has been developed. This approach enables facile processing of the titania/block copolymer surfactant precursor solution into optically activated, transparent, and crack-free fibers and planar waveguides with adjustable thickness. Stabilization of the structures occurs upon solvent evaporation by formation of a solid, glasslike material without heat treatment. These dye-activated, high refractive index, titania-based composites show efficient waveguiding and mirrorless lasing at low thresholds without the need of an ultralow refractive index support layer.