A chemically tethered organic/inorganic hybrid nanocomposite of poly (3-hexylthiophene) [P3HT] and TiO2 nanorods was successfully prepared through surface modification and in situ polymerization. In order to form an intimate contact between TiO2 and P3HT, a new layer of silane linker was coupled on TiO2 surface to replace the linoleic acid (LA). Subsequently, 3-hexylthiophene was insitu polymerized and anchored on the TiO2 surface through silane linker to form the hybrid nanocomposites. From Fourier transform infrared spectroscopy (FT-IR) spectra, the successful ligand exchange and polymerization on TiO2 surface was observed. The UV-Visible absorption of as prepared P3HT showed that the conjugated polymer and TiO2 has strong interaction with each other. The fluorescence quenching experiment proved that the chemically bonded nanocomposites have a more efficient charge transfer processes than simply blending them together.