In this work, we prepared a hybrid structure Co3S4@NCNT/NCHS using SiO2 nanospheres as a template. The structure is supported by hollow carbon spheres (NCHS), which are coated by Co3S4 nanoparticles and cross-linked N-doped carbon nanotubes. The combination of Co3S4 with N-doped carbon material significantly improves the electrocatalytic activity. In addition, the presence of N-doped carbon nanotubes induces more defects, which can regulate the electronic configuration of the material and improve its electrical conductivity. Therefore, Co3S4@NCNT/NCHS has good catalytic performance. At 10 mA cm−2, the OER overpotential of Co3S4@NCNT/NCHS is only 230 mV, which is lower than that of the commercial catalyst RuO2, and the ORR half-wave potential can reach 0.80 V. In the battery discharge test, Co3S4@NCNT/NCHS based ZABs can discharge continuously for 71.5 h, the specific capacity of 790.12 mA h g−1, power density of 113.09 m W cm−2, better than Pt/C+RuO2 battery. When the current density is 3 mA cm−2, ZABs assembled with Co3S4@NCNT/NCHS as catalyst can maintain a voltage gap of 0.62 V to 0.63 V within 300 h without significant change. When the current density is increased to 5 mA cm−2, ZABs based on Co3S4@NCNT/NCHS can be stably cycled for 300 h at a voltage gap between 0.80 V and 0.82 V.