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[Display omitted] • Ternary polymerization was firstly used to design eco-friendly acceptors. • PTer-N25 showed high performance in the IDTIC-based polymeric acceptors. • The all-PSC, fabricated by o -xylene solution, achieved a high PCE of 11.94%. • 2-Methylnaphthalene was firstly used as the additive to fabricate all-PSCs. The terpolymers based on indacenodithiophene dicyanindenone derivative, named as PTer-N10 , PTer-N25 and PTer-N50 , were designed and synthesized by incorporating naphthalenediimide derivative with 10%, 25% and 50% molar ratios as another electron-withdrawing unit, respectively. These terpolymers were used as the acceptors to prepare all-polymer solar cells (all-PSCs) with o -xylene as the solvent and 2-methylnaphthalene as the additive without any annealing treatment, which showed high power conversion efficiency (PCE). The terpolymer PTer-N25 possesses the highest light harvest, the best morphology, the highest and most balanced charge mobilities in blend film, so the all-PSC based on PM6: PTer-N25 achieved the highest PCE of 11.94%. This study indicates that ternary polymerization is an efficient strategy to obtain green-solvent processing polymeric acceptors, which can achieve high-performance all-PSCs. [ABSTRACT FROM AUTHOR]