Organic semiconductors show efficient electroluminescence which has led to their commercialization in light-emitting diodes (LEDs), however, they have been marred by the thorniest problem of solid-state quenching. Here, we report the synthesis and characterization of two fluorene-based blue amphiphile emitters containing triphenylamine or anthracene side groups and demonstrate formation of their hybrid meso-structured nanocomposites by sol-gel co-assembly with tetraethyl orthosilicate; and study the molecular interactions within the mesophases formed. The chromophore amphiphiles designed act as photonic active materials as well as structure-directing agents. The new blue luminescent fluorene-based amphiphile/silica co-assembled nanocomposite films have been successfully prepared with enhanced emission. Different kinds of light emitting devices based on these nanocomposites show efficiencies which are improved by several times compared with the corresponding pristine chromophore amphiphiles.