Abstract A micrometric silica modified with perylene derivative (SiO 2 –TES) has been prepared by hydrolysis–condensation reactions between silica and N,N’ -bis-(3-triethoxysilylpropyl)-perylene-tetracarboxyldiimide (P-TES) and utilized as filler in LLDPE films together with a compatibilizer. Spectroscopic analyses on SiO 2 –TES confirmed the grafting of P-TES on silica, while its amount was determined by thermogravimetric analysis. Solid state NMR provided information about the structure of silicon atoms involved in the condensation of SiO 2 and P-TES that resulted mainly in silicon atoms grafted with bi-dentate anchorages. UV–Vis and fluorescence analyses carried out on P-TES showed the ability of the dye to generate J-type aggregates in apolar solvents. The same analyses on SiO 2 –TES revealed the presence of both isolated and aggregated dye molecules grafted on silica surface, while on polymeric dispersions of SiO 2 –TES, they have shown only the presence of P-TES aggregates grafted to silica. Thanks to the direct correlation between optical properties (obtained both by UV–Vis and by fluorescence analyses) and the chemical environment of composites, the luminescent silica SiO 2 –TES could be used to estimate the filler dispersion extent in different microcomposite polymer materials.