AbstractThe fundamental understanding and precise control of catalytic sites are challenging yet essential to explore advanced electrocatalysts for the formic acid oxidation reaction (FAOR). Herein, this work demonstrates a new and promising catalyst prototype of antiperovskite‐type PdFe3N which possesses ordered and isolated Pd sites. The as‐synthesized PdFe3N/N‐rGO exhibits significant enhancement in catalytic activity, robust stability, and Fe anti‐dissolution properties when compared with PdFe3/rGO and Pd/C. Density functional theory (DFT) calculations reveal that isolated and ordered Pd sites are beneficial for high formate coverage and thus suppressing CO formation/poisoning. Moreover, the strong Fe–N covalent bonds improve the vacancy formation energy of Fe, which ensures superior Fe anti‐dissolution properties. Beyond offering a promising candidate for catalyzing FAOR, these findings provide deeper insights into the structure of CO tolerance relationships and benefit the theory‐guided design of highly efficient catalysts.