Hybrid materials obtained from organo-bridged silsesquioxane precursors have attracted much attention due to the possibility of tailoring the pore structure, framework composition, and morphologies over a wide range. Lanthanide complexes have long been known to give sharp, intense emission lines upon ultraviolet light irradiation. In recent years, the luminescence properties of lanthanide complexes supported on silica matrix have been studied extensively because their photophysical properties could be modified by interaction with the host structure. A novel 2, 6-diaminopyridine/silica nanocomposite thin film with ordered mesostructure was synthesized via a simple sol-gel assembly of silsesquioxane containing a bridged 2, 6-diaminopyridine function. Lanthanide complex/silica nanocomposite thin film was obtained by introducing lanthanide ion into the hybrid materials via a ligand exchange reaction. XRD, TEM, and N2 adsorption measurements were employed to characterize the mesostructure. The detailed luminescence studies showed that, compared with the conventional lanthanide complex/sol-gel hybrid material, our prepared lanthanide complex/silica nanocomposite thin films exhibited improved photophysical properties. Reference (1) G. Kickelbick. Angew. Chem. Int. Ed. 2004, 43, 3102-3104. (2) Sato, S.; Wada, M. Bull. Chem. Soc. Jpn. 1970, 43, 1955-1962. (3) Serra, O. A.; Rosa, I. L. V.; Medeiros, C. L.; Zaniquell, M. E. D. J. Lumin. 1994, 60&61, 112-114.