Soluble conjugated polymers based on 3,5-didecanyldithieno[3,2-b:2',3'-d] thiophene-single-bond (1), double-bond (2), and triple-bond linked (3)-were synthesized by palladium(0)-catalyzed Stille coupling reaction and oxidation polymerization. The thermal, absorption, emission, and electrochemical properties of these polymers were examined; the effect of the link pattern was studied. All polymers exhibit decomposition temperatures over 295 degrees C and glass-transition temperatures in the range of 137-202 degrees C. The absorption spectra of 1, 2, and 3 in thin films exhibit absorption maxima at 381, 584, and 444 rim, respectively. Polymer I exhibits intense green emission located at 510 nm in film, whereas polymers 2 and 3 are nonemissive both in solution and in film due to H-aggregate. Cyclic voltammograms of polymers 1, 2, and 3 display irreversible oxidation waves with onset oxidation potentials at 1.73, 0.78, and 1.03 V versus Ag+/Ag, respectively. Theory calculation on model compounds suggests that the dihedral angle decreases in the order of 1 > 3 > 2. On reducing the dihedral angle, the polymer exhibits a longer absorption maximum, a smaller bandgap, a less oxidizing potential and fluorescence quench, due to more coplanar and more pi-electron delocalized backbone structure. Polymer solar cells were fabricated based on the blend of polymer 2 and methanofullerene [6,6]-phenyl C61-butyric acid methyl ester (PCBM). The power conversion efficiency of 0.45% was achieved under AM 1.5, 100 mW cm(-2) using polymer 2:PCBM (1:2, w/w) as active layer. (c) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2843-2852, 2009