Poly (2,5-dimethoxy-p-phenylenevinylene) (dMeOPPV) has been formed in the intergallery spacing of a montmorillonite by introducing the (2,5-dimethoxy-1,4-phenylene) bis(methylene-S-tetrahydrothiophenium) monomer by ion exchange, increasing the basicity of the solid aluminosilicate with Cs+ and subsequent heating at 200 degrees C. dMeOPPV@montmorillonite was characterized by optical spectroscopy, FT-IR spectroscopy, solid-state C-13 NMR, photoluminescence, and chemical analysis. All the data are compatible with that reported in the literature for pure dMeOPPV. The dMeOPPV polymer incorporated inside montmorillonite exhibits a green light emission which makes the organic polymer very attractive for its application in polymer light-emitting diodes (PLEDs). The new polymeric material can be submitted to laser irradiation ( laser power, 10 mJ pulse(-1)) under oxygen without decomposition.