Long‐term stable and high active catalysts for oxygen reduction reaction (ORR) are required for the commercialization of proton exchange membrane fuel cells (PEMFCs). Platinum (Pt) catalyst is the preferred choose for ORR, but the stability and activity of existing Pt catalyst are unsatisfactory for the commercialization of PEMFCs. Here the ternary Pt–Au–Ni/C and binary Pt–Ni/C are synthesized by a rapid microwave‐assisted polyol reduction. The Pt–Au–Ni/C exhibits superior ORR activity to both of Pt–Ni/C and commercial Pt/C. Moreover, the Pt–Au–Ni/C exhibited the long‐term stability in both of half‐cell and single‐cell accelerated degradation tests. The above results indicate that the addition of Au into binary Pt–Ni catalyst can not only enhance the stability but also improve the electrocatalytic activity.

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An N-doped graphitic carbon layer was for the first time introduced to greatly enhance the durability of a PtNi3/C alloy catalyst in an acidic environment.