π-Conjugated polymers (CPs) have broad applications in high-performance optoelectronics, energy storage, sensors and biomedicine. However, developing green and efficient methods to precisely synthesize alternating CP structures on a large scale remains challenging and critical for their industrialization. Here a room-temperature, scalable and homogeneous Suzuki–Miyaura-type polymerization reaction is developed with broad generality validated for 24 CPs including donor–donor, donor–acceptor and acceptor–acceptor connectivities, yielding device-quality polymers with high molecular masses. Furthermore, the polymerization protocol significantly reduces homocoupling structural defects, yielding more structurally regular and higher-performance electronic materials and optoelectronic devices than conventional thermally activated polymerizations. Experimental and theoretical studies reveal that a borate transmetalation process plays a key role in suppressing protodeboronation, which is critical for large-scale structural regularity. Thus, these results provide a general polymerization tool for the scalable production of device-quality CPs with alternating structural regularity.

π-共轭聚合物（CP）在高性能光电子、储能、传感器和生物医学领域具有广泛的应用。然而，开发绿色高效的方法来大规模精确合成交替CP结构对于其工业化仍然具有挑战性和关键性。这里开发了一种室温、可扩展且均相的 Suzuki-Miyaura 型聚合反应，该反应具有广泛的通用性，经过验证，适用于 24 种 CP，包括供体-供体、供体-受体和受体-受体连接，产生具有高分子量的设备质量聚合物。此外，该聚合方案显着减少了自偶联结构缺陷，比传统的热活化聚合产生结构更规则、性能更高的电子材料和光电器件。实验和理论研究表明，硼酸盐金属转移过程在抑制原脱硼过程中起着关键作用，这对于大规模结构规律性至关重要。因此，这些结果为大规模生产具有交替结构规律的器件质量 CP 提供了通用聚合工具。