Head-to-tail regioregular poly(3-heptanoylthiophene) (PHOT) was synthesized by Ni-catalyzed polycondensation of the 2,2-dimethyl-1,3-propanediol-protected Grignard monomer followed by deprotection. Cyclic voltammetric (CV) study demonstrates that the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of PHOT are 0.5 eV lower in energy than those of the head-to-tail poly(3-hexylthiophene) (HT-P3HT). Their optical band gaps are essentially the same. Incomplete photoluminescence (PL) quenching was observed in thin films of the 1:1 blend of PHOT and HT-P3HT. PHOT displayed a glass transition at ∼269 °C and decomposed at ∼300 °C according to differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Wide-angle X-ray diffraction (WAXD) study showed that PHOT exists in a not highly ordered state in solid films especially in the π-stacking direction. Only p-channel activity was observed in field-effect transistors (FETs) for PHOT. The hole mobility was on the order of 10−4 cm2 V−1 s−1. Photovoltaic devices with an active layer of 1:1 blend of PHOT and PC71BM had a power conversion efficiency (PCE) of ∼0.5%. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010