The preparation of poly(ρ-phenylene vinylene) (PPV) encapsulated in a mesoporous silica, MCM-41, is reported. In situ polymerization of xylylene bis(tetrahydrothiophenium chloride) yields a highly luminescent, yellow powder with a fluorescence spectrum matching that of unencapsulated PPV. Nitrogen adsorption isotherms show that the pore size of the PPVloaded MCM-41 is significantly smaller than that of empty MCM-41 and a polymer loading of ca. 8% by weight is obtained by thermogravimetric analysis. Photoluminescence data for the encapsulated PPV are presented.