ConspectusIn the last three decades, p-type (hole-transporting) organic and polymeric semiconductors have achieved great success in terms of materials diversity and device performance, while the development of n-type (electron-transporting) analogues greatly lags behind, which is limited by the scarcity of highly electron-deficient building blocks with compact geometry and good solubility. However, such n-type semiconductors are essential due to the existence of the p-n junction and a complementary metal oxide semiconductor (CMOS)-like circuit in organic electronic devices. Among various electron-deficient building blocks, imide-functionalized arenes, such as naphthalene diimide (NDI) and perylene diimide (PDI), have been proven to be the most promising ones for developing n-type organic and polymeric semiconductors. Nevertheless, phenyl-based NDI and PDI lead to sizable steric hindrance with neighboring (hetero)arenes and a high degree of backbone distortion in the resultant semiconductors, which greatly limits their microstructural ordering and charge transport. To attenuate the steric hindrance associated with NDI and PDI, a novel imide-functionalized heteroarene, bithiophene imide (BTI), was designed; however, the BTI-based semiconductors suffer from high-lying frontier molecular orbital (FMO) energy levels as a result of their electron-rich thiophene framework and monoimide group, which is detrimental to n-type performance.In this Account, we review a series of BTI derivatives developed via various strategies, including ring fusion, thiazole substitution, fluorination, cyanation, and chalcogen substitution, and elaborate the synthesis routes designed to overcome the synthesis challenges due to their high electron deficiency. After structural optimization, these BTI derivatives can not only retain the advantages of good solubility, a planar backbone, and small steric hindrance inherited from BTI but also have greatly suppressed FMO levels. These novel building blocks enable the construction of a great number of n-type organic and polymeric semiconductors, particularly acceptor-acceptor (or all-acceptor)-type polymers, with remarkable performance in various devices, including electron mobility (μe) of 3.71 cm2 V-1 s-1 in organic thin-film transistors (OTFTs), a power conversion efficiency (PCE) of 15.2% in all-polymer solar cells (all-PSCs), a PCE of 20.8% in inverted perovskite solar cells (PVSCs), electrical conductivity (σ) of 0.34 S cm-1 and a power factor (PF) of 1.52 μW m-1 K-2 in self-doped diradicals, and σ of 23.3 S cm-1 and a PF of ∼10 μW m-1 K-2 in molecularly n-doped polymers, all of which are among the best values in each type of device. The structure-property-device performance correlations of these n-type semiconductors are elucidated. The design strategy and synthesis of these novel BTI derivatives provide important information for developing highly electron-deficient building blocks with optimized physicochemical properties. Finally, we offer our insights into the further development of BTI derivatives and semiconductors built from them.