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Although there are several electron-donating (D) units, only the classic benzo[1,2-b4,5-b']dithiophenes (BDT) unit was utilized to develop D-π-A-type copolymers for high-voltage organic photovoltaic (OPV) cells. Hence, in this work, we chose two tricyclic D units, BDT and benzo[1,2-b4,5-b']difurans (BDF), together with one pentacyclic ring, dithieno[2,3-d;2',3'-d']benzo[1,2-b;4,5-b']dithiophenes (DTBDT), to comprehensively study the effect of different D units on the optoelectronic properties and photovoltaic performance. By copolymeriz