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The limited number of reactions amenable to solid\u2010state execution necessitates a continued pursuit of novel topochemical transformations. Here, we report the first example of a topochemical alkyne nitrile oxide cycloaddition (TANOC) reaction, a spontaneous and regiospecific [3\u00a0+\u00a02] cycloaddition that directly converts a monomer to an isoxazole\u2010linked polymer in a SCSC fashion at room temperature. We overcome the inherent reactivity of nitrile oxides through strategic steric protection, enabling the design of a stable monomer amenable to crystallization. Detailed structural analysis of both monomer and polymer by single\u2010crystal X\u2010ray diffraction, coupled with comprehensive spectroscopic and kinetic studies, confirms the formation of an isoxazole\u2010backbone polymer. Notably, despite an initially unfavorable monomer packing, significant voids within the crystal lattice facilitate a \u223c118\u00b0 rotation of the propargyl unit, achieving the precise geometry for spontaneous reaction. This unprecedented thermal topochemical transformation expands the toolkit for solid\u2010state polymer synthesis, offering a versatile platform for constructing functional materials where the isoxazole linkages can be readily transformed into diverse functionalities.<\/jats:p>","DOI":"10.1002\/anie.202520947","type":"journal-article","created":{"date-parts":[[2025,11,3]],"date-time":"2025-11-03T07:36:26Z","timestamp":1762155386000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Topochemical Alkyne Nitrile Oxide Cycloaddition for Polymer Synthesis"],"prefix":"10.1002","volume":"64","author":[{"given":"Rahul","family":"Singh","sequence":"first","affiliation":[{"name":"School of Chemistry Indian Institute of Science Education and Research Thiruvananthapuram  Thiruvananthapuram 695551 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Anjana","family":"Siddharthan","sequence":"additional","affiliation":[{"name":"School of Chemistry Indian Institute of Science Education and Research Thiruvananthapuram  Thiruvananthapuram 695551 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4005-3655","authenticated-orcid":false,"given":"Kana M.","family":"Sureshan","sequence":"additional","affiliation":[{"name":"School of Chemistry Indian Institute of Science Education and Research Thiruvananthapuram  Thiruvananthapuram 695551 India"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,11,2]]},"reference":[{"key":"e_1_2_6_1_1","doi-asserted-by":"publisher","DOI":"10.1039\/C2CS35343A"},{"key":"e_1_2_6_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.9b00398"},{"key":"e_1_2_6_3_1","first-page":"201","volume-title":"Templates in Chemistry I","author":"MacGillivray L. 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