In this study, we report on the preparation of uniform hollow-structured Co/CoS₂ nanoparticles encapsulated within N, S co-doped carbon nanotubes (NSCNTs). The bifunctional electrocatalytic performance of these materials for ORR and OER is significantly enhanced by the synergistic effect of strongly coupled Mott-Schottky junctions in the Co/CoS₂ nanoparticles and abundant heteroatom dopants in the CNT shells. The Co/CoS₂/NSCNT exhibits half-wave potential of 0.890 V vs. RHE and overpotential of 359 mV at 10 mA cm-2 for ORR and OER, respectively. Moreover, rechargeable ZAB assembled with the Co/CoS₂/NSCNT catalyst delivers a specific capacity of 746 mAh gZn-1 and a peak power density of 156.8 mW cm-2, which exceed those values of precious metal-based ZAB (673 mAh gZn-1 and 136.9 mW cm-2, respectively). These findings demonstrate the potential of Co/CoS₂/NSCNTs as high-performance electrocatalysts for rechargeable ZABs, and provide insights into the design of efficient and cost-effective electrocatalysts for energy storage applications.