(Graph Presented) The synthesis of poly[3-(4-n-octyl)-phenylthiophene] (POPT) from Grignard Metathesis (GRIM) is reported. GRIM POPT is found to have favorable electronic, optical, and processing properties for organic photovoltaics (OPVs). Space-charge limited current and field effect transistor measurements for POPT yielded hole mobilities of 1 × 10-4 cm2/(V s) and 0.05 cm2/(V s), respectively. Spincasting GRIM POPT from chlorobenzene yields a thin film with a 1.8 eV band gap, and PC61BM:POPT bulk heterojection devices provide a peak performance of 3.1%. Additionally, an efficiency of 2.0% is achieved in an all-polymer, bilayer OPV using poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-(1-cyanovinylene) phenylene] (CNPPV) as an acceptor. This state-of-the-art all-polymer device is analyzed in comparison to the analogous poly(3-hexylthiophene) (P3HT)/CNPPV device. Counter to expectations based on more favorable energy level alignment, greater active layer light absorption, and similar hole mobility, P3HT/CNPPV devices perform less well than POPT/CNPPV devices with a peak efficiency of 0.93%. © 2009 American Chemical Society.