The PdPtCo core-shell nanostructure, fabricated via galvanic replacement by rapidly incorporating Pd into PtCo nanoalloys at room temperature, excels in alcohol oxidation (AOR). Synergistic effects lower Pt electron density, promoting C-C cleavage, while increased Co coverage reduces COads adsorption, enhancing CO tolerance. This work offers a novel strategy for high-performance AOR catalysts.