Two new wide-bandgap polythiophenes, i.e., poly[5,5′-bis(2-hexyldecyl)-(2,2′-bithiophene)-4,4′-dicarboxylate-alt-5,5′-3-chloro-2,2′-bithiophene] (PDCBT-Cl) and poly[5,5′-bis(2-hexyldecyl)-(2,2′-bithiophene)-4,4′-dicarboxylate-alt-5,5′-3,3′-dichloro-2,2′-bithiophene] (PDCBT-2Cl) comprising 3-chloro-2,2′-bithiophene and 3,3′-dichloro-2,2′-bithiophene moieties, respectively, were synthesized for fullerene-free polymer solar cells (PSCs). For comparison, three other polymers based on [2,2′-bithiophene]-4,4′-dicarboxylate (DCBT), i.e., PDCBT, PDCBT-F, and PDCBT-2F with 2,2′-bithiophene, 3-fluoro-2,2′-bithiophene, and 3,3′-difluoro-2,2′-bithiophene as comonomers, respectively, were also prepared. PSC devices were fabricated with these polymers as donor materials and ITIC-Th1 as acceptor. The incorporation of chlorine (Cl) or fluorine (F) atoms into polymers both efficiently downshifted the highest occupied molecular orbital (HOMO) energy levels, leading to higher open-circuit voltage (Voc) in the PSCs. Owing to…