Two conjugated copolymers, poly{4,7-[5,6-bis(octyloxy)]benzo(c)(1,2,5)thiadiazole-alt-4,8-di(2-ethylhexyloxyl)benzo[1,2-b:3,4-b]dithiophene} (P1) and poly(2-{5-[5,6-bis(octyloxy)-4-(thiophen-2-yl)benzo(c)(1,2,5)thiadiazol-7-yl] thiophen-2-yl}-4,8-di(2-ethylhexyloxyl)benzo(1,2-b:3,4-b)dithiophene) (P2), composed of benzodithiophene and 5,6-dioctyloxybenzothiadiazole derivatives with or without thiophene units were synthesized via a Stille cross-coupling polymerization reaction. These copolymers are promising for applications in bulk heterojunction solar cells because of their good solubility, proper thermal stability, moderate hole mobility, and low band gap. The photovoltaic properties of these copolymers were investigated on the basis of blends of the different polymer/(6,6)-phenyl-C71-butyric acid methyl ester (PC71BM) weight ratios under AM1.5G illumination at 100 mW/cm2. The device with indium tin oxide/poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate)/P2:PC71BM (1 : 2 w/w)/Ca/Al gave a relatively better photovoltaic performance with a power conversion efficiency of 1.55%. (C) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012