A novel materials design procedure based on the co-doping of metal nanoparticle and azo dye compound (MNPADC) is developed to improve the properties of functional molecules. The synthesized materials were characterized by transmission electron micrograph (TEM), ultraviolet-visible absorption spectra (UV-Vis) and fluorescence spectra (FS). It was found that the fluorescence intensity of methyl orange (MO) was enhanced by 5 times in the aqueous composite system doped with silver nanoparticles whereas it was reduced by 15% and 20% in composite films with co-mixing and coating structures, respectively. The results indicate that the properties of functional molecules can be greatly improved in composite film with supra molecular structure and that the procedure presented here is effective.