Molecularly Engineered DBC‐Pyrene Hole Transport Material Achieves Dual Passivation‐Transport Functionality for Efficient and Robust Perovskite Solar Cells

Persistent interfacial defects and instability remain key limitations for high‐performance perovskite solar cells (PSCs), motivating the development of multifunctional materials that can simultaneously enable efficient charge transport and defect passivation. Here, we report a molecularly engineered dibenzo[g,p]chrysene (DBC)‐based core molecule winged by N‐(4‐methoxyphenyl)pyren‐1‐amine units, SP‐07, designed to operate in two distinct yet complementary roles: as a dopant‐free hole‐transport material (HTM) and as an interfacial passivation layer. Owing to its planar conjugated core and electron‐rich functional groups, SP‐07 exhibits high intrinsic hole mobility (∼28.7 × 10 −4 cm 2 /V·s), uniform film formation, and efficient charge extraction. When employed as a standalone HTM, SP‐07‐based PSCs achieve a stabilized power conversion efficiency (PCE) of 21.7% and demonstrate exceptional operational stability under continuous illumination at 85°C, outperforming spiro‐OMeTAD‐based reference devices. On the other hand, acting as a passivation layer, SP‐07 constructively mitigates under‐coordinated Pb 2+ /halide defects, reduces trap‐assisted recombination, improves surface hydrophobicity, and maintains perovskite crystallinity, resulting in devices with a champion PCE exceeding 23%. Outstandingly, passivated devices retain ∼95% of their initial PCE after 1000 h of continuous operation under thermal and illumination stress and maintain structural integrity under ambient conditions for 30 days. These findings demonstrate that the dual functionality of SP‐07 enables synergistic improvements in both efficiency and long‐term stability, providing a promising strategy for advancing PSCs.