AbstractContinuous flow methods are utilized in conjunction with direct arylation polymerization (DArP) for the scaled synthesis of the roll‐to‐roll compatible polymer, poly[(2,5‐bis(2‐hexyldecyloxy)phenylene)‐alt‐(4,7‐di(thiophen‐2‐yl)‐benzo[c][1,2,5]thiadiazole)] (PPDTBT). PPDTBT is based on simple, inexpensive, and scalable monomers using thienyl‐flanked benzothiadiazole as the acceptor, which is the first β‐unprotected substrate to be used in continuous flow via DArP, enabling critical evaluation of the suitability of this emerging synthetic method for minimizing defects and for the scaled synthesis of high‐performance materials. To demonstrate the usefulness of the method, DArP‐prepared PPDTBT via continuous flow synthesis is employed for the preparation of indium tin oxide (ITO)‐free and flexible roll‐coated solar cells to achieve a power conversion efficiency of 3.5% for 1 cm2 devices, which is comparable to the performance of PPDTBT polymerized through Stille cross coupling. These efforts demonstrate the distinct advantages of the continuous flow protocol with DArP avoiding use of toxic tin chemicals, reducing the associated costs of polymer upscaling, and minimizing batch‐to‐batch variations for high‐quality material.