Two new photoluminescent (PL) surfactants consisting of hydrophobic/PL diphenylpyreneamine chromophores and hydrophilic oligo(ethylene glycol) segments have been synthesized and characterized. The PL surfactants induce the molecular self-assembly of hydrolyzed 1,2-bis(triethoxysilyl)ethane (BTSE) via evaporation induced self assembly (EISA) under mildly acidic conditions into PL mesostructured nanocomposites. The mesostructure forming capability for both PL surfactants were confirmed by XRD. PL spectra of the final functionalized nanocomposites suggest that the PL surfactants are confined within the nanometer regime of the rigid organosilica matrix.