A novel rigid donor monomer, indacenodithieno[3,2‐b]thiophene (IDTT), containing linear alkyl chains, is reported. Its copolymer with benzothiadiazole is an excellent p‐type semiconductor, affording a mobility of 6.6 cm2 V−1 s−1 in top‐gated field‐effect transistors with pentafluorobenzenethiol‐modified Au electrodes. Electrode treatment with solution‐deposited copper(I) thiocyanate (CuSCN) has a beneficial hole‐injection/electron‐blocking effect, further enhancing the mobility to 8.7 cm2 V−1 s−1.

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Three copolymers based alkylated indacenodithieno[3,2-b]thiophene (IDTT) are reported.