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Chlorinated 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...