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Here, we report the first metal\u2010free, self\u2010sensitized molecular photocatalyst capable of driving visible\u2010light\u2010induced CO\n                    <jats:sub>2<\/jats:sub>\n                    \u2010to\u2010HCOO\n                    <jats:sup>\u2212<\/jats:sup>\n                    conversion via a consecutive photoinduced electron transfer (ConPET) mechanism. The rationally designed BPI\u2010OMe, featuring an electron\u2010donating group, demonstrates exceptional performance under visible light irradiation, achieving a formate production rate of 27.51\u00a0mmol g\n                    <jats:sup>\u22121<\/jats:sup>\n                    \u00a0h\n                    <jats:sup>\u22121<\/jats:sup>\n                    with &gt; 99% selectivity. This outstanding activity stems from its optimized electronic properties: a low excitation energy (2.98\u00a0eV), a long\u2010lived charge\u2010separated anion radical state (\n                    <jats:italic>\u03c4<\/jats:italic>\n                    = 806.94\u00a0ns), a high\u2010energy SOMO level (\u22123.47\u00a0eV), and strong CO\n                    <jats:sub>2<\/jats:sub>\n                    binding affinity (\u22120.147\u00a0eV). In situ ESR and ultrafast spectroscopic analyses reveal the ConPET process: sequential photon absorption enables electron transfer from ascorbic acid to BPI\u2010OMe, generating BPI\u2010OMe, followed by electron delivery to CO\n                    <jats:sub>2<\/jats:sub>\n                    to form CO\n                    <jats:sub>2<\/jats:sub>\n                    <jats:sup>\u2212<\/jats:sup>\n                    , which is subsequently converted to formate through a hydrogen atom transfer. This work not only represents a breakthrough in metal\u2010free PCO2R but also provides a general molecular design strategy based on multi\u2010photon charge accumulation for enabling challenging solar\u2010to\u2010chemical transformations.\n                  <\/jats:p>","DOI":"10.1002\/anie.1083625","type":"journal-article","created":{"date-parts":[[2026,5,19]],"date-time":"2026-05-19T16:34:23Z","timestamp":1779208463000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Metal\u2010Free Photocatalytic CO\n                    <sub>2<\/sub>\n                    Reduction to Formate Driven by Visible Light via a Consecutive Photoinduced Electron Transfer Mechanism"],"prefix":"10.1002","volume":"65","author":[{"given":"Xianjun","family":"Yin","sequence":"first","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing Advanced Innovation Center for Soft Matter Science and Engineering College of Chemistry Beijing University of Chemical Technology  Beijing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jingjie","family":"Hu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing Advanced Innovation Center for Soft Matter Science and Engineering College of Chemistry Beijing University of Chemical Technology  Beijing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Heng","family":"Wu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing Advanced Innovation Center for Soft Matter Science and Engineering College of Chemistry Beijing University of Chemical Technology  Beijing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Cui","family":"Xu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing Advanced Innovation Center for Soft Matter Science and Engineering College of Chemistry Beijing University of Chemical Technology  Beijing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bin","family":"Liu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing Advanced Innovation Center for Soft Matter Science and Engineering College of Chemistry Beijing University of Chemical Technology  Beijing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7852-3325","authenticated-orcid":false,"given":"Hui\u2010Qing","family":"Peng","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing Advanced Innovation Center for Soft Matter Science and Engineering College of Chemistry Beijing University of Chemical Technology  Beijing 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