Single-atom Fe catalysts are considered as the promising catalysts for oxygen reduction reaction (ORR). However, the high electronegativity of the symmetrical coordination N atoms around Fe site generally results in too strong adsorption of *OOH intermediates on the active site, severely limiting the catalytic performance. Herein, a heteroatom pair synergetic modulation strategy is proposed to tailor the coordination environment and spin state of Fe sites, enabling breaking the shackles of unsuitable adsorption of intermediate products on the active centers toward a more efficient ORR pathway. The unsymmetrically Co and B heteroatomic coordinated Fe single sites supported on an N-doped carbon (FeBCo/NC) catalyst perform excellent ORR activity with high half-wave potential (E-1/2) of 0.891 V and a large kinetic current density (J(k)) of 60.6 mA cm(-2), which is several times better than those of commercial Pt/C catalysts. By virtue of in situ electrochemical impedance and synchrotron infrared spectroscopy, it is observed that the optimized Fe sites can effectively accelerate the evolution of O-2 into the *O intermediate, overcoming the sluggish OO bond cleavage of the *OOH intermediate, which is responsible for fast four-electron reaction kinetics.
