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Here, a molecular conformation engineering strategy is developed to construct TBBP, which features a strengthened electron donor, a moderately twisted conformation, extended \u03c0\u2010conjugation, and a robust molecular skeleton free of labile olefinic \u03c0\u2010bridges. TBBP exhibits excellent photostability, broadband second near\u2010infrared (1000\u20131600\u00a0nm) emission, and efficient photothermal conversion (42.17%). Supramolecular assembly with DSPE\u2010PEG2000 affords stable TBBP nanomicelles, TBBP NPs, that selectively generate superoxide radicals (O\n                    <jats:sub>2<\/jats:sub>\n                    <jats:sup>\u2212\u2022<\/jats:sup>\n                    ) and retain potent Type I photodynamic therapy (PDT) activity under hypoxia. Photoactivated TBBP NPs further induce mitochondrial dysfunction and caspase\u20103\/GSDME\u2010mediated immunogenic pyroptosis, promoting dendritic cell maturation and CD8\n                    <jats:sup>+<\/jats:sup>\n                    T cell infiltration. In a bilateral 4T1 tumor model, TBBP NPs enable high\u2010contrast second near\u2010infrared (NIR\u2010II) imaging, while synergistic Type I PDT and photothermal therapy elicit systemic antitumor immunity, achieving 92.0% primary tumor inhibition and 47.7% distant tumor inhibition. This work establishes a molecular conformation engineering strategy and extends its functionality through supramolecular assembly, synergistically integrating NIR\u2010II imaging, hypoxia\u2010tolerant Type I phototherapy, and photoimmunotherapy, thereby providing a generalizable molecular design principle for the development of next\u2010generation multifunctional organic phototheranostic agents.\n                  <\/jats:p>","DOI":"10.1002\/adma.75395","type":"journal-article","created":{"date-parts":[[2026,10,15]],"date-time":"2026-10-15T08:49:12Z","timestamp":1792054152000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Hypoxia\u2010Tolerant Supramolecular Nanomicelles for Pyroptosis\u2010Enhanced NIR\u2010II Phototheranostics"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-6080-4540","authenticated-orcid":false,"given":"Xing","family":"Wang","sequence":"first","affiliation":[{"name":"Institute of Intelligent Materials Southeast University  Nanjing China"},{"name":"School of Intelligent Science and Engineering Southeast University  Wuxi China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kunyan","family":"Dong","sequence":"additional","affiliation":[{"name":"Institute of Intelligent Materials Southeast University  Nanjing China"},{"name":"School of Intelligent Science and Engineering Southeast University  Wuxi China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0003-3532-9447","authenticated-orcid":false,"given":"Zhichao","family":"Wang","sequence":"additional","affiliation":[{"name":"Institute of Intelligent Materials Southeast University  Nanjing China"},{"name":"School of Intelligent Science and Engineering Southeast University  Wuxi China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0001-5851-7657","authenticated-orcid":false,"given":"Yuqi","family":"Tang","sequence":"additional","affiliation":[{"name":"Institute of Intelligent Materials Southeast University  Nanjing China"},{"name":"School of Intelligent Science and Engineering Southeast University  Wuxi China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9042-360X","authenticated-orcid":false,"given":"Quan","family":"Li","sequence":"additional","affiliation":[{"name":"Institute of Intelligent Materials Southeast University  Nanjing China"},{"name":"School of Intelligent Science and Engineering Southeast University  Wuxi 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