We demonstrate an efficient strategy to anchor poly(3-hexylthiophene) (P3HT) onto zinc oxide (ZnO) surfaces. Synthesis of a novel triethoxysilane-terminated regioregular P3HT is herein reported and supported by thorough characterization. Three triethoxysilane-terminated P3HTs of different molar masses were prepared via a hydrosilylation reaction from allyl-terminated P3HT. MALDI-TOF and H-1 NMR were performed to characterize the polymer and show that around 80% of the chains are end-functionalized. These polymers were then grafted onto the ZnO nanorods to create a macromolecular self-assembled monolayer. This versatile technique could be subsequently applied to different metal oxide surfaces, such as silicon, titanium, or indium-tin oxide, and represents a new one-pot strategy based on triethoxysilane coupling reaction. Importantly, the influence of the molar mass on the grafting density and the polymer shell thickness was studied via thermo gravimetric analysis and transmission electron microscopy. The optical properties of the hybrid materials were determined by UV-visible absorption and photoluminescence to show a quenching effect of P3HT fluorescence by ZnO when grafted. This electronic transfer associated with an improved miscibility of the ZnO@P3HT, makes these hybrid materials suitable candidates for photovoltaic applications. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 30-38