Hybrid materials composed of transition-metal compounds and nitrogen-doped carbonaceous supports are promising electrocatalysts for various electrochemical energy conversion devices, whose activity enhancements can be attributed to the synergistic effect between metallic sites and N dopants. While the functionality of single-metal catalysts is relatively well-understood, the mechanism and synergy of bimetallic systems are less explored. Herein, the design and fabrication of an integrated flexible electrode based on NiCo S /graphitic carbon nitride/carbon nanotube (NiCo S @g-C N -CNT) are reported. Comparative studies evidence the electronic transfer from bimetallic Ni/Co active sites to abundant pyridinic-N in underlying g-C N and the synergistic effect with coupled conductive CNTs for promoting reversible oxygen electrocatalysis. Theoretical calculations demonstrate the unique coactivation of bimetallic Ni/Co atoms by pyridinic-N species (a Ni, Co-N moiety), which simultaneously downshifts their d-band center positions and benefits the adsorption/desorption features of oxygen intermediates, accelerating the reaction kinetics. The optimized NiCo S @g-C N -CNT hybrid manifests outstanding bifunctional performance for catalyzing oxygen reduction/evolution reactions, highly efficient for realistic zinc-air batteries featuring low overpotential, high efficiency, and long durability, superior to those of physical mixed counterparts and state-of-the-art noble metal catalysts. The identified bimetallic coactivation mechanism will shed light on the rational design and interfacial engineering of hybrid nanomaterials for diverse applications.