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Here, we propose a thermally activated lithium formate (LiHCOO) buried interface strategy that triggers in situ pseudo\u2010halide diffusion, thereby simultaneously reconstructing the SnO\n                    <jats:sub>2<\/jats:sub>\n                    \/perovskite interface and regulating perovskite nucleation and growth. High\u2010temperature treatment transforms LiHCOO from its low\u2010temperature hexagonal polymorph to a metastable monoclinic phase with a more open molecular packing structure, thereby enabling deeper HCOO\n                    <jats:sup>\u2212<\/jats:sup>\n                    diffusion into the buried perovskite. Diffused HCOO\n                    <jats:sup>\u2212<\/jats:sup>\n                    strongly interacts with undercoordinated Pb\n                    <jats:sup>2+<\/jats:sup>\n                    sites, inhibiting pinhole formation, reducing trap density, compensating for halide vacancy related defects, and releasing residual tensile strain. Meanwhile, LiHCOO modification passivates the SnO\n                    <jats:sub>2<\/jats:sub>\n                    surface by reducing oxygen vacancies and hydroxyl defects, improving interfacial electrical properties. This enhances the built\u2010in potential of perovskite devices from 0.91 to 1.00 V while optimizing energy level alignment. Ultimately, the optimized perovskite solar cell achieved a champion efficiency of 25.48%, with an open\u2010circuit voltage of 1.213 V and a fill factor of 82.57%, while also demonstrating outstanding long\u2010term stability. This work reveals polymorph\u2010mediated pseudo\u2010halide diffusion as a novel approach to low\u2010loss and robust perovskite photovoltaics.\n                  <\/jats:p>","DOI":"10.1002\/advs.75864","type":"journal-article","created":{"date-parts":[[2026,5,29]],"date-time":"2026-05-29T14:20:51Z","timestamp":1780064451000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["In Situ Pseudo\u2010Halide Diffusion Enables Buried Interface Regulation and Crystallinity Enhancement in Perovskite Solar Cells"],"prefix":"10.1002","volume":"13","author":[{"given":"Chao","family":"Gao","sequence":"first","affiliation":[{"name":"College of Chemistry and Chemical Engineering Huangshan University  Huangshan P. R. China"},{"name":"Institute of Solar Energy, and Key Laboratory of Artificial Structures and Quantum Control (Ministry of Education) School of Physics and Astronomy Shanghai Jiao Tong University  Shanghai P. R. 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