Abstract: | A pyromellitic diimide building block, 2,6‐bis(2‐decyltetradecyl)?4,8‐di(thiophen‐2‐yl)pyrrolo[3,4‐f]isoindole‐1,3,5,7(2H,6H)‐tetraone ( 4 ), is synthesized. Based on this building block and other electron‐rich units such as 2,2′‐bithiophene, thieno[3,2‐b]thiophene and 4,8‐bis(dodecyloxy)benzo[1,2‐b:4,5‐b′]dithiophene, three conjugated polymers P1 , P2 , and P3 are prepared in good yield via Stille coupling polymerization. These new copolymers have good solubility in common organic solvents and exhibit good thermal stability. The optical, electrochemical, and thermal properties of these polymers P1–P3 are carefully investigated, and their applications in solution‐processed organic field‐effect transistors are also studied. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2454–2464 |