Novel poly(3-hexylthiophene)/titania hybrids were synthesized by the sol-gel process using titanium(TV) isopropoxide as a precursor in the presence of silane-bearing poly(3-hexylthiophene), which was prepared from the copolymerization of 3-hexylthiophene and 3-thienylmethyl-N-triethoxylsilylpropyl amide monomers. The chemical structure of these materials was characterized by FT-IR and H-1 NMR. SEM micrographs demonstrated that the TiO2 nanoparticles were evenly distributed within the hybrid materials. The energy levels of the hybrid material were determined from cyclic voltammagrams (CV) and UV-vis spectra. Photoluminescence spectra imply that the photo-induced electron transfer is more efficient in silane-bearing poly(3-hexylthiophene)/TiO2 than in poly(3-hexylthiophene)/TiO2. (c) 2005 Elsevier B.V. All rights reserved.