Conjugated poly(2,5-thienylene ethynylene) (PTE)/silica nanocomposites with cubic and lamellar mesostructures have been synthesized. Surfactant directed assembly coorganized 2,5-diiodothiophene monomer and palladium-based catalyst within a silica matrix. Subsequent polymerization initiated by exposing the monomer/catalyst/silica nanostructures to acetylene gas resulted in the formation of an ordered, mesostructured poly(2,5-thienylene ethynylene)/silica nanocomposite as determined by XRD, UV-vis, FTIR, and TEM experiments. Mesostructured PTE with 287m2/g surface area is obtained after silica removal. Further polymerization of PTE oligomers occurs after exposure to acetylene gas due to active Pd catalyst attached to the polymer chains. This novel approach provides a unique route to synthesize mesostructured conjugated polymer/inorganic nanocomposites and porous mesostructured PTE.