A series of soluble donor-acceptor conjugated polymers comprising of phenothiazine donor and various benzodiazole acceptors (i.e., benzothiadiazole, benzoselenodiazole, and benzoxadiazole) sandwiched between hexyl-thiophene linkers were designed, synthesized, and used for the fabrication of polymer solar cells (PSC). The effects of the benzodiazole acceptors on the thermal, optical, electrochemical, and photovoltaic properties of these low-bandgap (LBG) polymers were investigated. These LBG polymers possessed large molecular weight (M-n) in the range of 3.85-5.13 x 10(4) with high thermal decomposition temperatures, which demonstrated broad absorption in the region of 300-750 nm with optical bandgaps of 1.80-1.93 eV. Both the HOMO energy level (-5.38 to -5.47 eV) and LUMO energy level (-3.47 to -3.60 eV) of the LBG polymers were within the desirable range of ideal energy level. Under 100 mW/cm(2) of AM 1.5 white-light illumination, bulk heterojunction PSC devices containing an active layer of electron donor polymers mixed with electron acceptor [6,6]-phenyl-C-61-butyric acid methyl ester (PC61BM) or [6,6]-phenyl-C-71-butyric acid methyl ester (PC71BM) in different weight ratios were investigated. The best performance of the PSC device was obtained by using polymer PP6DHTBT as an electron donor and PC71BM as an acceptor in the weight ratio of 1:4, and a power conversion efficiency value of 1.20%, an open-circuit voltage (V-oc) value of 0.75 V, a short-circuit current (J(sc)) value of 4.60 mA/cm(2), and a fill factor (FF) value of 35.0% were achieved. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4823-4834, 2010