The development of n-type organic semiconductors critically relies on the design and synthesis of highly electron-deficient building blocks with good solubility and small steric hindrance. We report here a strongly electron-deficient dithienylpyrazinediimide (TPDI) and its n-type semiconducting polymers. The pyrazine substitution leads to the resulting polymers with much lower-lying lowest unoccupied molecular orbital (LUMO) levels and improved backbone planarity compared to the reported dithienylbenzodiimide (TBDI)- and fluorinated dithienylbenzodiimide (TFBDI)-based polymer analogues, thus yielding n-type transport character with an electron mobility up to 0.44 cm2 V–1 s–1 in organic thin-film transistors. These results demonstrate that dithienylpyrazinediimide is a highly promising electron-deficient building block for constructing high-performance n-type polymers and the incorporation of pyrazine into imide-functionalized (hetero)­arenes is an effective strategy to develop n-type polymers with deep-lying frontier molecular orbital (FMO) levels for organic optoelectronic devices.