Abstract Terpolymers consisting of three monomers with one electron donor unit and two electron acceptor units are promising p-type polymers for polymer solar cells (PSCs) because the incorporation of a third monomer into a copolymer backbone provides synergetic effect on physical properties such as absorption ability, charge transport, and photovoltaic performance. Currently, novel p-type terpolymers need to be developed for high-efficiency PSCs, which can be processed with eco-friendly non-halogenated solvents. In this study, a new series of terpolymers composed of 4,8-di(2,3-didecylthiophen-5-yl)-benzo[1,2-b:4,5-b′]dithiophene (BDT), 4,7-di(thien-2-yl)-5,6-difluoro-2,1,3-benzothiadiazole (DTffBT), and benzo[1,2-c:4,5-c′]dithiophene-4,8-dione (BDD) segments was synthesized and characterized for high-performance PSCs processed with non-halogenated solvents. PBDTBD terpolymers (i.e., PBDTBD-25, PBDTBD-50, and PBDTBD-75) were synthesized by adjusting different ratios of DTffBT to BDD segment (25%, 50%, and 75% of DTffBT). PBDTBD terpolymers exhibited excellent solubility in non-halogenated solvents. The optical, electrochemical, and morphological properties of PBDTBD terpolymers were successfully controlled by modulating the molar ratio of DTffBT and BDD. Moreover, a PBDTBD-50:IT-4F blended film showed homogeneous film with a favorable face-on orientation. The PBDTBD-50:IT-4F blended film showed excellent hole and electron mobility, which resulted in a superior carrier balance. PBDTBD-50-based PSCs, processed with o-xylene, achieved the highest PCE of 10.03%, which is four times higher than those of copolymer-based PSCs. The novel terpolymers composed of one electron donor unit and two electron acceptor units are expected to make a considerable contribution to the development of high-performance PSCs.