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Here, we report the design and characterization of PhotoNiR, an engineered azurin\u2010based protein incorporating a red copper center and a lanthanide\u2010binding tag (LBT). This dual\u2010metal system enables photoredox reduction of nitrite to nitric oxide via a proposed donor\u2010f\u2010electron\u2010acceptor (D\u2010f\u2010A) electron transfer mechanism. Upon photoirradiation, aromatic residues in the LBT donate electrons to the lanthanide ion, which relays them to the Cu(II) center, reducing it to Cu(I). The reduced Cu(I)\u2010PhotoNiR catalyzes the reduction of NO<jats:sub>2<\/jats:sub><jats:sup>\u2212<\/jats:sup>, and the generated NO subsequently reacts with free cysteine residues to form S\u2010nitrosothiol (SNO) species. Spectroscopic and structural characterization confirmed that the copper center retains the properties of a red copper site and that the lanthanide\u2010binding tag supports efficient electron transfer. This work represents one of the first examples of a D\u2010f\u2010A mechanism in a protein system, demonstrating the potential of integrating metalloprotein engineering with lanthanide photochemistry to develop novel photoenzymes for light\u2010driven catalysis.<\/jats:p>","DOI":"10.1002\/chem.202500143","type":"journal-article","created":{"date-parts":[[2025,3,11]],"date-time":"2025-03-11T17:02:31Z","timestamp":1741712551000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Engineering a Hetero\u2010Bimetallic Azurin Photoenzyme for Photoredox Nitrite Reduction and SNO Adduct Formation"],"prefix":"10.1002","volume":"31","author":[{"given":"Binbin","family":"Su","sequence":"first","affiliation":[{"name":"Department: Institute of Biochemical Engineering Key Laboratory of Medical Molecule Science and Pharmaceutics Engineering of Ministry of Industry and Information Technology School of Chemistry and Chemical Engineering Beijing Institute of Technology  Beijing 102488 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0784-9715","authenticated-orcid":false,"given":"Yang","family":"Yu","sequence":"additional","affiliation":[{"name":"Department: Institute of Biochemical Engineering Key Laboratory of Medical Molecule Science and Pharmaceutics Engineering of Ministry of Industry and Information Technology School of Chemistry and Chemical Engineering Beijing Institute of Technology  Beijing 102488 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Haiping","family":"Liu","sequence":"additional","affiliation":[{"name":"Department: School of Life Sciences University of Science and Technology of China  Hefei Anhui 230026 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Chun","family":"Li","sequence":"additional","affiliation":[{"name":"Department: Key Laboratory for Industrial Biocatalysis Ministry of Education Department of Chemical Engineering Tsinghua University  Beijing 100081 China"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2025,3,15]]},"reference":[{"unstructured":"\u00a0","key":"e_1_2_7_1_1"},{"doi-asserted-by":"publisher","key":"e_1_2_7_2_2","DOI":"10.1039\/C8CC01297K"},{"doi-asserted-by":"publisher","key":"e_1_2_7_3_2","DOI":"10.1021\/acs.accounts.1c00719"},{"doi-asserted-by":"publisher","key":"e_1_2_7_4_2","DOI":"10.1021\/acs.accounts.4c00129"},{"doi-asserted-by":"publisher","key":"e_1_2_7_5_2","DOI":"10.1021\/jacs.4c04618"},{"unstructured":"\u00a0","key":"e_1_2_7_6_1"},{"year":"2024","author":"Raps F. 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