Macromolecular Innovations for High‐Performance Organic and Perovskite Solar Cells

ABSTRACT Macromolecular materials have emerged as key components in both organic photovoltaics (OPVs) and perovskite solar cells (PSCs). This review highlights recent advancements in macromolecular materials and their role in improving OPVs and PSCs. In PSCs, these materials contribute to multiple functional layers, including hole‐transport layers (HTLs), electron‐transport layers (ETLs), interfacial layers (IFLs), and polymeric additives. Dopant‐free polymeric HTLs, such as PTAA derivatives and poly(carbazole phosphonic acid), enhance charge transfer and passivation, while non‐fullerene polymer ETLs improve electron mobility and mitigate perovskite degradation. Polymeric additives also aid in crystallization control, defect passivation, and mechanical reinforcement, enhancing moisture resistance, thermal stability, and overall device lifespan. In OPVs, advances in conjugated polymer donors and acceptors have significantly enhanced charge transport, exciton dissociation, and light absorption. Non‐fullerene acceptors (NFAs), particularly Y‐series derivatives, have enabled record‐breaking power conversion efficiencies (PCEs) exceeding 20%. The integration of polymer acceptors and ternary blend strategies further strengthens phase stability and mechanical durability. Additionally, polymeric charge transport layers improve energy level alignment, suppress charge recombination, and extend device longevity. This review underscores the critical role of macromolecular materials in enhancing the performance and stability of OPVs and PSCs, driving the development of more efficient and sustainable solar energy solutions .