A new electron acceptor building block, 3,6-di(pyridin-2-yl)pyrrolo[3,4-c ]pyrrole-1,4(2H ,5H)-dione (DBPy), is used to construct a donor-acceptor polymer, PDBPyBT. This polymer exhibits a strong self-assembly capability, to form highly crystalline and oriented thin films with a short π–π stacking distance of 0.36 nm. PDBPyBT shows ambipolar charge-transport performance in organic thin-film transistors, reaching a record high electron-mobility value of 6.30 cm2 V−1 s−1. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Record High Electron Mobility of 6.3 cm2V−1s−1 Achieved for Polymer Semiconductors Using a New Building Block