A soluble conjugated alternating 3,5-didecanyldithieno[3,2-b:2',3'-d]thiophene-thiophene copolymer was synthesized by palladium(0)-catalyzed Stille coupling reaction. The thermal, absorption, emission, electrochemical, and photovoltaic properties of the polymer were examined. A weight-average molecular weight around 6.2 x 10(4) and a polyclispersity, index of 1.8 was estimated for the polymer using gel permeation chromatography. The polymer exhibits good thermal stability with decomposition temperature of 340 degrees C and glass-transition temperature of 136 degrees C. The polymer shows strong absorption peaked at 505 nm in diluted solution and 518 nm in thin film with an optical band gap 2.0 eV. The polymer exhibits intense emission located at 550 nm in solution and 603 nm in film. The HOMO and LUMO energies of the polymer were estimated to be -5.4 and -3.4 eV, respectively, by cyclic voltammetry. Polymer solar cells were fabricated based on the blend of the polymer and methanofullerene [6,6]-phenyl C61-butyric acid methyl ester (PCBM). The power conversion efficiency of 0.7% was achieved under AM 1.5, 100 mW/cm(2) using polymer:PCBM (1:4, w/w) as active layer. (C) 2009 Elsevier Ltd. All rights reserved.