Strong Electron‐Withdrawing Molecules Facilitating π–π Stacking and Charge Transfer Complexes at Buried Interface and Enabling an Inverted PSC with Open‐Circuit Voltage of 1.2 V

defects through coordination and hydrogen bonding, suppressing ion migration and carrier nonradiative recombination. Meanwhile, p-type doping by F4TCNQ elevates the SAMs work function, reducing the hole extraction barrier by 0.12 eV and enhancing charge transfer driving force. Optimized devices achieve a champion power conversion efficiency of 25.91% with a high open-circuit voltage of 1.202 V, while retaining 91% efficiency after 1000 h of maximum power point tracking, attributed to stabilized ion dynamics and robust interfacial adhesion. This work demonstrates molecular bridging as a scalable strategy for high-performance photovoltaics.