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Here, we create a biotic\u2013abiotic hybrid system where the biosynthesized cadmium sulfide quantum dots (CdS QDs) are interfaced with the extracellular electron transfer (EET) pathway of\n                    <jats:italic>Shewanella oneidensis<\/jats:italic>\n                    MR\u20101, forming a bioelectronic photocommutator. This biotic\u2013abiotic hybrid enables light\u2010dependent, bidirectional control of electron transfer. Under 405\u00a0nm illumination, the system enhances outward EET, while switching to inward electron flow under 450\u00a0nm illumination. We elucidate the switching mechanism through photoelectrochemical, spectroscopic, XPS, and electrochemiluminescence experiments, revealing that the connection between CdS and EET proteins regulates the energy band structure of CdS via defect\u2010state passivation, thus establishing two distinct electron transfer circuits. This switching mechanisim allows the QD\u2010protein nanohybrid to function as the photocommutator on microbial electron transport pathway. Based on this principle, we have constructed a bioelectrochemical system, the microbial photovoltaic cell (MPC), that can be charged and discharged with light, and further demonstrated its application as a thin\u2010film, flexible power source. This work provides a nano\u2010bio interface for the active regulation of bioelectrochemical processes, opening an avenue for programmable biotic\u2013abiotic nanohybrids in bioenergy storage and bioelectronics.\n                  <\/jats:p>","DOI":"10.1002\/anie.7229401","type":"journal-article","created":{"date-parts":[[2026,9,23]],"date-time":"2026-09-23T06:16:44Z","timestamp":1790144204000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Bioelectronic Photocommutator to Regulate Extracellular Electron Transfer Circuits for Microbial Photovoltaic Energy Storage"],"prefix":"10.1002","author":[{"given":"Bing","family":"Li","sequence":"first","affiliation":[{"name":"School of Chemistry and Molecular Engineering Nanjing Tech University  Nanjing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tianrui","family":"Liu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of 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