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Biomimetic catalysts have drawn broad research interest owing to both high specificity and excellent catalytic activity. Herein, we report a series of biomimetic catalysts by the integration of biomolecules (hemin or ferrous phthalocyanine) onto well-defined Au/CeO2, which leads to the high-performance CO oxidation catalysts. Strong electronic interactions among the biomolecule, Au, and CeO2 were confirmed, and the CO uptake over hemin-Au/CeO2 was roughly about 8 times greater than Au/CeO2. Based on the Au/CeO2(111) and hemin-Au/CeO2(111)