摘要： Random conjugated terpolymers (RCTs) not only promote great comprehension and realization for state-of-the-art high effective non-fullerene polymer solar cells (OSCs) but also offer a simple and practical synthetic strategy. However, the photovoltaic properties of RCTs yet lagged behind that of the donor-acceptor alternating copolymer, especially in the additive-free devices. Hence, we developed two feasible “double acceptor type” random conjugated terpolymers, PBDB-TAZ20 and PBDB-TAZ40. The additive-free OSCs based on PBDB-TAZ20:ITIC and PBDB-TAZ40:ITIC exhibit decent efficiencies of 12.34% and 11.27%, respectively, which both surpass the PBDB-T:ITIC-based device. For the RCTs, the reasonably weakened crystallinity and reduced phase separation degree are demonstrated to help improve charge transport, reduce bimolecular recombination and thus enhance the photovoltaic performance of the additive-free OSCs. The results imply that adding a third moiety into the D-A polymer donors provides a simple but efficient synthetic approach for high-performance OSCs.