Perovskite solar cells (PSCs) have achieved over 27% efficiency, rivaling silicon cells due to the excellent optical properties of lead halide perovskites (LHPs)^[1]. As an absorbing material, LHPs possess unique and excellent optical properties, including low production cost, tunable band gap, broad absorption, low exciton binding energy, and high charge-carrier mobility^[2]. However, defects in the bulk (intrinsic) and interfaces of perovskite materials, as well as Li⁺ migration (especially in n–i–p regular architecture), caused by LiTFSI salt, used to enhance the conductivity and hole mobility of spiro-OMeTAD, can significantly impact device performance and stability^[3]. To date, numerous passivation molecules have been developed to enhance perovskite device performance by interacting with undercoordinated Pb²⁺ defects or by inhibiting Li⁺ ion migration^[4]. However, these strategies typically target only one type of degradation pathway at a time. To the best of our knowledge, a molecule capable of simultaneously passivating Pb²⁺ defects and suppressing Li⁺ ion migration has not yet been reported.

Herein, we report a rationally designed meso-crowned porphyrin derivative ([12]-C-4POR) featuring dual macrocyclic binding sites, i.e., a porphyrin core for undercoordinated Pb²⁺ and a crown ether unit selective for Li⁺ to suppress surface defects and mitigate lithium-ion migration simultaneously^[5]. We found that the porphyrin core is strongly bonded with Pb²⁺ while the ether part captures the Li⁺ and suppresses its migration. The time-of-flight secondary ion mass spectrometry (TOF-SIMS) shows that [12]-C-4POR based device showed much lower levels of Li⁺ migration, with only limited diffusion compared to the control device. The incorporation of [12]-C-4POR into perovskite films significantly reduced the trap-state density and suppressed non-radiative recombination, leading to improved charge-carrier dynamics. Devices treated with [12]-C-4POR delivered a champion PCE of 23.14%, surpassing the control device (21.6%), along with enhanced open-circuit voltage (V_OC) and fill factor (FF). More importantly, the passivated devices retained ∼95% of their initial PCE after 800 h of continuous operation, compared to ∼55% for the control. Furthermore, [12]-C-4POR-treated device showed significantly better thermal and environmental stabilities compared to the control cell. This study demonstrates a dual-site host–guest passivation strategy as an effective route to improve both efficiency and operational stability of PSCs.