AbstractTransition‐metal catalysts with metal nanoparticles (NPs) as active sites are widely utilized in various reactions. In this work, we report the atomic decoration of Pt upon Co NPs for enhanced catalytic performances in oxidation esterification. Systematical characterizations imply the single‐atom nature and homogeneous distribution of Pt throughout the formed single‐atom alloy (SAA). The synergistic interactions between Pt and Co lead to significant charge redistribution and up‐shifted density of states (DOS) toward the Fermi level, which are verified favorable for the adsorption and activation of substrates. The esterification performances of Pt1Co@C are evaluated in the transformation of 54 kinds of aromatic alcohols (5‐hydromethylfurfural, furfural, and benzyl alcohols) into the corresponding mono‐ and diesters. Pt1Co@C shows not only remarkably enhanced reactivity but also reliable durability in both batch and continuous flow reactors. Mechanism investigations clearly reveal the rapid transformation of 5‐hydromethylfurfural over Pt1Co@C through a simplified route with reduced energy barriers.