Comprehensive SummaryChlorinated conjugated polymers are rarely reported in ambipolar and n‐type organic thin‐film transistors (OTFTs), mainly due to the lack of chlorinated strong electron‐deficient building blocks. Herein, we report three new chlorine (Cl)‐ and cyano (CN)‐ substituted (E)‐1,2‐di(thiophen‐2‐yl)ethane building blocks and their copolymers P2Cl1CNTVT‐DPP, P4Cl1CNTVT‐DPP and P2Cl2CNTVT‐DPP. P2Cl1CNTVT‐DPP and P2Cl2CNTVT‐DPP had nearly planar backbone geometries, mixture of edge‐on and face‐on orientation and deeper energy levels, while P4Cl1CNTVT‐DPP had a twist backbone geometry, face‐on orientation and shallower energy levels. As a result, P2Cl1CNTVT‐DPP exhibited ambipolar characteristic with hole mobility (μh) of 0.70 cm2·V–1·s–1 and electron mobility (μe) of 0.84 cm2·V–1·s–1 and P2Cl2CNTVT‐DPP exhibited n‐type characteristic with μe of 0.64 cm2·V–1·s–1, while P4Cl1CNTVT‐DPP exhibited the lowest μe of 0.36 cm2·V–1·s–1. The devices based on P2Cl2CNTVT‐DPP exhibited good stability after being stored for 10 d in air. The results demonstrate that by rational molecular design, chlorinated polymers with low cost can be applied to high‐performance ambipolar and n‐type OTFTs.