Herein, a proof-of-concept study on the evaluation of Fe nanoparticles (Fe NPs) encapsulated by nitrogen-doped carbon to Fe single atoms (Fe SAs) for boosting the oxygen reduction reaction (ORR) catalytic activity toward Zn-air batteries was reported. Specifically, unlike Fe SAs encapsulated by nitrogen-doped carbon (Fe SAs@NC), the Fe SAs and Fe NPs co-embedded in nitrogen-doped carbon (Fe SAs/NPs@NC) derived from a pyrolysis and acid dissolution protocols exhibits excellent ORR performance with good stability and remarkable methanol tolerance in alkaline solutions. Combining a series of experimental analyses, the strong interaction between the atomically dispersed Fe-N_x and adjacent Fe NPs in altering the electronic structure of isolated Fe-N_x sites could weaken the binding energies of the ORR intermediates on Fe SAs/NPs@NC, resulting in an enhanced electrocatalytic kinetics than Fe SAs@NC and Pt/C catalysts. This strategy not only offers a new way for synthesis highly efficient Fe-N/C catalysts toward ORR, but also provides the new insights into the understanding of the mechanism of adjacent Fe NPs encapsulated by nitrogen-doped carbon to Fe SAs sites.