Insight into the modulation effect of oxygen reduction reaction (ORR) active centers is of profound significance but remains a great challenge. Here, we designed Co, Fe dual-metal single-atom sites (CoFe-DSAs/NC) uniformly anchored on nitrogen-doped multiwalled carbon nanotubes for boosting ORR performance through regulating the 4d electronic orbitals of the Co-N4 active site. Mechanism studies revealed that for the first time the neighboring Fe-N4 atomic sites were able to regulate the d-band center of Co-N4 single-atom active centers while maintaining the balance of adsorption-desorption affinity for O2 and oxygen-containing species on Co-N4, thereby resulting in a superior ORR performance with a positive half-wave potential (0.90 V vs RHE). The assembled zinc-air battery based on CoFe-DSAs/NC exhibited an increased open-circuit voltage (1.48 V) and an elevated specific capacity (782.33 mAh·g-1). The work provides a new clue for reasonably designing high-performance ORR catalysts through adjusting the d-band center of active sites.