The development of highly efficient and stable oxygen reduction electrocatalysts and revealing their underlying catalytic mechanism are crucial in expanding the applications of metal‐air batteries. Herein, an excellent FeCo alloy nanoparticles (NPs)‐decorated N‐doped mesoporous carbon electrocatalyst (FeCo/NC) for oxygen reduction reaction, prepared through the pyrolysis of a dual metal containing metal‐organic framework composite scaffold is reported. Benefiting from the highly exposed bimetal active sites and the carefully designed structure, the Fe_0.25Co_0.75/NC‐800 catalyst exhibits a promising electrocatalytic activity and a superior durability, better than those of the state‐of‐the‐art catalysts. Suggested by both the X‐ray absorption fine structures and the density functional theoretical calculation, the outstanding catalytic performance is originated from the synergistic effects of the bimetallic loading in NC catalysts, where the electronic modulation of the Co active sites from the nearby Fe species leads to an optimized binding strength for reaction intermediates. This work demonstrates a class of highly active nonprecious metals electrocatalysts and provides valuable insights into investigating the structure–performance relationship of transition metal‐based alloy catalysts.