Conjugated copolymers based on benzodithiophene (BDT) derivatives and thiophene-quinoxaline-thiophene (TQT) segments represent an efficient class of light harvesting materials for organic photovoltaic (OPV) applications. Commonly, BDT-TQT copolymers are synthesized by Stille cross-coupling polymerization. In this study, alkoxy and thienyl functionalized alternating BDT-alt-TQT copolymers are synthesized by direct arylation polymerization (DArP), using Ozawa conditions. An extensive optimization of the reaction conditions such as the catalytic system, solvent, temperature, base, and the concentration of the catalyst is accomplished. The optical and electrochemical properties of the copolymers obtained by DArP are compared to the reference polymers synthesized by Stille cross-coupling polymerization. Finally, the optimized BDT-alt-TQT copolymers are incorporated into organic solar cells as electron donors. The solar cells of the DArP copolymers exhibit power conversion efficiencies up to 80% (rel.) of their Stille cross coupling analogues. (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1457-1467