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To address this issue, we report a new strategy, namely employing a spin\u2010orbit charge transfer intersystem crossing (SOCT\u2010ISC), to unlock the triplet manifold in conjugated microporous polymers (CMPs). Using a postsynthetic [2 +\u00a02] cycloaddition\u2010retroelectrocyclization (CA\u2010RE) reaction, we precisely control the cyano number in the polymer backbone. This chemical modification induces a critical orthogonal molecular torsion, which maximizes spin\u2010orbit coupling (SOC) and minimizes the singlet\u2010triplet energy gap (\u0394\n                    <jats:italic>E<\/jats:italic>\n                    <jats:sub>ST<\/jats:sub>\n                    ). Femtosecond transient absorption spectroscopy confirms the efficient triplet generation by torsion engineering. Consequently, the optimized photocatalyst achieves a hydrogen peroxide (H\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    ) production rate of 5.01\u00a0mmol g\n                    <jats:sup>\u22121<\/jats:sup>\n                    h\n                    <jats:sup>\u22121<\/jats:sup>\n                    in pure water and a rate of 101.26\u00a0mmol g\n                    <jats:sup>\u22121<\/jats:sup>\n                    h\n                    <jats:sup>\u22121<\/jats:sup>\n                    in a benzyl alcohol\u2010coupled system, with a solar\u2010to\u2010chemical conversion (SCC) efficiency of 0.62%, and an outdoor production reaches 5\u00a0mmol L\n                    <jats:sup>\u22121<\/jats:sup>\n                    daily. This work leverages torsion engineering to harness triplet excitons, demonstrating the successful overcoming of thermodynamic barriers in artificial photosynthesis.\n                  <\/jats:p>","DOI":"10.1002\/anie.6174836","type":"journal-article","created":{"date-parts":[[2026,9,9]],"date-time":"2026-09-09T03:41:21Z","timestamp":1788925281000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Manipulating Spin\u2010Orbit Coupling in Conjugated Microporous Polymers Through Torsion Engineering to Generate Efficient Triplet Excitons for High\u2010Performance Photocatalysis"],"prefix":"10.1002","author":[{"given":"Danfeng","family":"Wang","sequence":"first","affiliation":[{"name":"School of Petrochemical Engineering Changzhou University  Changzhou China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Heman","family":"Xu","sequence":"additional","affiliation":[{"name":"School of Petrochemical 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