Facile Access to IDT‐Based Acceptor via Direct C–H Arylation and Its Exploration in Binary and Ternary Organic Solar Cells

The pursuit of efficient and environmentally benign synthetic routes for electron acceptors via is vital to advancing the commercialization of organic solar cells (OSCs). In this study, we leverage a direct C–H arylation strategy to synthesis a novel A‐D‐π‐D‐A‐type acceptor ( D1 ), which offers significant advantages in step and atom economy, along with a reduced environmental impact compared to conventional cross‐coupling methods. When combined with the polymer donor PM6, the optimized PM6:D1 binary devices attained a power conversion efficiency (PCE) of 9.85%. Furthermore, capitalizing on the well‐aligned energy levels and complementary absorption with the benchmark blend PM6:Y6, D1 was successfully incorporated as a third component to fabricate ternary OSCs. The resulting PM6:Y6:D1 devices exhibited more balanced charge transport, enhanced exciton dissociation, and improved photovoltaic parameters, yielding a champion PCE of 16.58%. This work highlights the considerable potential of C–H arylation as a green synthesis method for constructing high‐performance acceptors and offers key insights for designing efficient multi‐component organic photovoltaic systems.