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Here we disclose that a bioinspired peptide\u2010phosphonium salt (PPS) catalytic system successfully enables precise desymmetrization of phosphinic acids through synergistic ion\u2010pairing and hydrogen\u2010bonding interactions. This strategy affords multifunctional platform molecules bearing P(V)\u2010stereocenters with excellent enantiocontrol and broad compatibility (43 examples, up to 92% yield, up to &gt;99% ee) at very low catalyst loading (1 mol%). Furthermore, the P(V)\u2010chiral building blocks undergo stereospecific derivatization to access structurally diverse phosphinates (27 examples, up to 75% yield, up to &gt;99% ee) and tertiary phosphine oxides (10 examples). Mechanistic studies reveal that the stereochemical origin is from a semi\u2010enclosed chiral cavity, where dynamic electrostatic and hydrogen\u2010bonding interactions synergistically orchestrate the stereodetermining transition state. The two\u2010stage desymmetrization\u2013derivatization process establishes a versatile platform for modular synthesis of valuable P(V)\u2010stereogenic pharmaceuticals and functional molecules.<\/jats:p>","DOI":"10.1002\/anie.202510513","type":"journal-article","created":{"date-parts":[[2025,8,8]],"date-time":"2025-08-08T05:28:16Z","timestamp":1754630896000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":14,"title":["Bioinspired Peptide\u2010Phosphonium Salt Catalysis Unlocks Asymmetric Desymmetrization of Phosphoryl Acids: Programmable Synthesis of P(V)\u2010Stereogenic Molecules"],"prefix":"10.1002","volume":"64","author":[{"given":"Siqun","family":"Yang","sequence":"first","affiliation":[{"name":"Key Laboratory of Green Chemistry &amp; Technology of Ministry of Education College of Chemistry, Sichuan University  29 Wangjiang Road Chengdu 610064 P.R. 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