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Optimizing the electronic structure of Pt-based alloys has emerged as an effective strategy to further improve their catalytic oxygen reduction reaction (ORR) performance, yet this remains challenging. Here, we have successfully tuned the electronic structure of ordered PtCoFe nanoparticles by incorporating the third component (Fe) into a bimetallic ordered PtCo alloy and manipulating its content. With the merits of the optimum electronic structure and the favorable composition, as well as the robust ordered structure, the as-prepared or