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Here, we report a protein\u2010supported single\u2010atom catalytic platform that enables orthogonal decoupling of first\u2010 and second\u2010shell effects. Structurally invariant Pt(Glu)\n                    <jats:sub>2<\/jats:sub>\n                    units were covalently anchored onto protein scaffolds, while protein conformational transitions selectively modulated the surrounding spatial microenvironment without perturbing the metal active site. Reversible catalytic modulation spanning \u223c65% activity range was achieved solely through conformational cycling, without any detectable change to the metal coordination environment. Kinetic analysis revealed that activity changes were dominated by variations in substrate affinity (Km) rather than intrinsic turnover, as confirmed by nearly identical activation energies between folded and unfolded states from Arrhenius analysis. Fluorescence tracking and molecular dynamics simulations further supported that protein folding enhances substrate accessibility and spatial preorganization around the catalytic center. These findings provide an experimentally grounded basis for second\u2010shell design in artificial catalysts, offering a rational strategy to bridge the activity gap between synthetic single\u2010atom systems and natural metalloenzymes.\n                  <\/jats:p>","DOI":"10.1002\/smll.76025","type":"journal-article","created":{"date-parts":[[2026,9,30]],"date-time":"2026-09-30T14:31:17Z","timestamp":1790778677000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Orthogonal Decoupling of First\u2010 and Second\u2010Shell Contributions in Protein\u2010Supported Single\u2010Atom Catalysis"],"prefix":"10.1002","author":[{"given":"Haiyan","family":"Li","sequence":"first","affiliation":[{"name":"School of Chemistry and Chemical Engineering Key Laboratory of Theoretical Organic Chemistry and Function Molecule Ministry of Education Hunan Provincial Key Laboratory of Controllable Preparation and Functional Application of Fine Polymers Hunan University of Science and Technology  Xiangtan China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0008-4912-879X","authenticated-orcid":false,"given":"Ruishu","family":"Xu","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Key Laboratory of Theoretical Organic Chemistry and Function Molecule Ministry of Education Hunan Provincial Key Laboratory of Controllable Preparation and Functional Application of Fine Polymers Hunan University of Science and Technology  Xiangtan China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jiangtao","family":"Cai","sequence":"additional","affiliation":[{"name":"School of Life and Health Sciences Hunan University of Science and Technology  Xiangtan China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhennian","family":"Liu","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical 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