Poly [2-methoxy-5-(2'-ethyl-hexyloxy)-1,4phenylene vinylene] (MEH-PPV) covered by nanostructured silica shells were synthesized via sol-gel process and investigated after freeze-drying and heat-drying in vacuum. The freeze-dried sample consists of a light pink powder while the heat-dried sample presents a redder coarsegrained material. The freeze-dried sample was analyzed using small angle X-ray scattering (SAXS). Both samples were analyzed using photoluminescence (PL) and Raman spectroscopy at room temperature. The PL spectra presented relatively large red shifts compared with that of the MEH-PPV in tetrahydrofuran solution, which was taken as a reference sample. The energy shifts observed in the PL and Raman spectra strongly support an explanation based on denser packing conditions inside the nanostructured silica shells, which can effectively lead the polymer molecules to a higher interchain interaction via aggregate sites. (c) 2006 Wiley Periodicals, Inc.