π-Conjugated polymers (CPs) are widely used in the field of high-performance plastic electronics. However, the development of sustainable and efficient methods for synthesizing donor-acceptor (D–A)-type CPs remains challenging for their industrialization. In this study, we introduce a simple and rapid direct arylation polycondensation (DArP) technique for preparing various D–A benzotriazole-based π-CPs with high molecular weights under aerobic conditions in two hours. Additionally, the method demonstrates not only excellent yields but also copolymers with nearly defect-free structures. Via a minor modification involving the use of twenty or more equivalents of the base K2CO3 and refluxing the solvent, high molecular weight copolymers can be achieved in a short reaction time under oxygen and moisture conditions. Therefore, this finding presents a direct synthetic protocol that utilizes commercially available and air-stable catalyst precursors to produce high-quality π-CPs suitable for optoelectronic applications.