Perylene bisimide (PBI)-based acceptor polymers have been synthesized by the facile and environmental-friendly palladium-catalyzed direct arylation. The direct arylation using a bromothiophene-extended PBI monomer, which was designed for the direct arylaion, proceeded to yield PBI-based acceptor polymers (PPBI3T). As a result of screening the direct arylation conditions, PPBI3T with the number average molecular weight of 14,000 was successfully synthesized, and the spectroscopic and optoelectronic analysis demonstrated the synthesis of PPBI3T with the desired structure. The random compolymerization among naphthalene bisimide (NBI)-based monomer, PBI-based monomer, and 3,4-dimethylthiophene afforded the random copolymers composed of NBI- and PBI-based components (P(NBI3T-PBI3T)). The composition of each component was controlled by changing the monomer feed ratio, and furthermore, the optical and electrochemical properties of P(NBI3T-PBI3T) were also tunable by controlling the composition of each component. To the best of our knowledge, these results were the first accomplishment for the direct arylation synthesis of PBI-based acceptor polymers. (c) 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 3151-3158