Low optical bandgap conjugated polymers may improve the efficiency of organic photovoltaic devices by increasing the absorption in the visible and near infrared region of the solar spectrum, Here we demonstrate that condensation polymerization of 2,5-bis(5-trimethylstannyl-2-thienyl)-N-dodecylpyrrole and 4,7-dibromo-2,1,3-benzothiadiazole in the presence of Pd(PPh3)(2)Cl-2 as a catalyst affords a novel conjugated oligomeric material (PTPTB), which exhibits a low optical bandgap as a result of the alternation of electron-rich and electron-deficient units along the chain. By varying the molar ratio of the monomers in the reaction and fractionation of the reaction product, two different molecular weight fractions (PTPTB-I and PTPTB-II, see Experimental section) were isolated, containing 5-17 and 13-33 aromatic units respectively, as inferred from matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Thin films of PTPTB-I and PTPTB-II exhibit an optical bandgap of 1.60 and 1.46 eV, respectively. Photoinduced absorption (PIA) and photoluminescence spectroscopy of blends of PTPTB-I and a methanofullerene (1-(3-methoxycarbonyl)-propyl-1-phenyl-[6,6]C-61, PCBM) gave direct spectral evidence of the photoinduced electron-transfer reaction from PTPTB-I as a donor to the fullerene derivative as an acceptor. Thin PTPTB-I:PCBM composite films were sandwiched between indium tin oxide/poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonic acid) (ITO/PEDOT-PSS) and Al electrodes to prepare working photovoltaic devices, which show an open circuit voltage of 0.67 V under white-light illumination. The spectral dependence of the device shows an onset of the photocurrent at 1.65 eV (750 nm).