24.64%‐Efficiency MA‐Free Perovskite Solar Cell with V oc of 1.19 V Enabled by a Hinge‐Type Fluorine‐Rich Complex

High density of defects at interface severely affects the performance of perovskite solar cells (PSCs). Herein, cobalt (II) hexafluoro‐2,4‐pentanedionat (CoFAc), a hinge‐type fluorine‐rich complex, is introduced onto the surface of formamidinium cesium lead iodide (FACsPbI 3 ) film to address the issues of perovskite/Spiro‐OMeTAD interface. The existence of CoFAc passivates both organic cation and halide anion vacancies by establishing powerful hydrogen bonds with HC(NH 2 ) 2 + (FA + ) and strong ionic bonds with Pb 2+ in perovskite films. In addition, CoFAc serves as a connecting link to enhance interfacial hole‐transport kinetics via interacting with Spiro‐OMeTAD. Consequently, FACsPbI 3 PSCs with CoFAc modification display a champion power conversion efficiency (PCE) of 24.64% with a charming open‐circuit voltage ( V OC ) of 1.191 V, which is the record V OC among all the reported organic‐inorganic hybrid PSCs with TiO 2 as electron transport layer. Furthermore, CoFAc‐modified devices exhibit an outstanding long‐term stability, which can maintain 95% of their initial PCEs after exposure to ambient atmosphere for 1500 h without any encapsulation.