The resource shortage and high cost of noble metal catalysts are still obstacles to their widespread applications. Herein, under the guidance of DFT calculation results, a facile and effective strategy for synthesizing noble metal-free catalysts is used to construct heteroatoms co-doped carbon catalyst. The N, P, S tri-doped hollow carbon nanospheres (NPSCSs) are synthesized via template-induced polymer-derived strategy and carbonizationetching-carbonization process. The obtained NPSCSs display special hollow structure with large specific surface area of 1154.89 m(2)g(-1). As expect, NPSCSs as bifunctional oxygen catalyst exhibit high-performance electrocatalytic activity. More attractively, as the cathode catalysts of assembled the Zn-air batteries (ZABs), NPSCSs show high maximum power density and long cycle stability. This strategy providing a new way to obtain multiheteroatoms-doped electrocatalysts with excellent electrocatalytic activity and cycling stability.