An increasing demand for n-type and ambipolar semiconductors has emerged as a challenging task for the organic electronics community. However, to efficiently inject electrons to semiconductors requires a high electron affinity material that is still limited in scope to date. Herein, ethanediylidenebis(isoquinolinedione), an electron-deficient six-membered-ring imide containing building block, is developed. Using fused imide rings to bridge the arylene-vinylene conjugation pathway is conducive to charge delocalization in contrast to conventional rylene diimide based materials. Additionally, the bridging imide groups provide sites to form intramolecular hydrogen bonds, a feature that can further reduce the conformational disorder. Three polymers based on this building block have been synthesized, exhibiting ambipolar charge transport behaviors. The highest hole and electron mobilities of up to 0.138 and 0.0739 cm(2) V(-1)s(-1) were observed for a polymer with a fluorinated bithiophene subunit. Introducing bridged imide linkages to polymer backbones can extend the scope of rational design strategies for polymer semiconductors.