The development of oxygen reduction reaction (ORR) electrocatalysts based on earth‐abundant nonprecious materials is critically important for sustainable large‐scale applications of fuel cells and metal–air batteries. Herein, a hetero‐single‐atom (h‐SA) ORR electrocatalyst is presented, which has atomically dispersed Fe and Ni coanchored to a microsized nitrogen‐doped graphitic carbon support with unique trimodal‐porous structure configured by highly ordered macropores interconnected through mesopores. Extended X‐ray absorption fine structure spectra confirm that Fe‐ and Ni‐SAs are affixed to the carbon support via FeN4 and NiN4 coordination bonds. The resultant Fe/Ni h‐SA electrocatalyst exhibits an outstanding ORR activity, outperforming SA electrocatalysts with only Fe‐ or Ni‐SAs, and the benchmark Pt/C. The obtained experimental results indicate that the achieved outstanding ORR performance results from the synergetic enhancement induced by the coexisting FeN4 and NiN4 sites, and the superior mass‐transfer capability promoted by the trimodal‐porous‐structured carbon support.
