The construction and understanding of synergy in well-defined dual-atom active sites is an available avenue to promote multistep tandem catalytic reactions. Herein, we construct a dual-hetero-atom catalyst that comprises adjacent Cu-N4 and Se-C3 active sites for efficient oxygen reduction reaction (ORR) activity. Operando X-ray absorption spectroscopy coupled with theoretical calculations provide in-depth insights into this dual-atom synergy mechanism for ORR under realistic device operation conditions. The heteroatom Se modulator can efficiently polarize the charge distribution around symmetrical Cu-N4 moieties, and serve as synergistic site to facilitate the second oxygen reduction step simultaneously, in which the key OOH*-(Cu1 -N4 ) transforms to O*-(Se1 -C2 ) intermediate on the dual-atom sites. Therefore, this designed catalyst achieves satisfied alkaline ORR activity with a half-wave potential of 0.905 V vs. RHE and a maximum power density of 206.5 mW cm-2 in Zn-air battery.