Developing a high-efficienct, low-cost and stable non-noble-metal-based bifunctional electrocatalyst for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) as oxygen electrode material in the rechargeable zinc-air battery is crucial in renewable energy conversion technologies. In this work, nitrogen-doped hollow carbon sphere (NHCS) decorated with various nickel selenide (NixSe) nanoparticles had been designed and successfully prepared. Among them, the Ni0.85Se-NHCS with the highest percentage of Ni3+ could serve as a new efficient bifunctional electrocatalyst toward ORR/OER (with an onset potential of 0.850V for ORR and a potential of 1.583V at 10mAcm(-2) for OER) in an alkaline medium. Furthermore, the assembled Zn-air battery coupled with Ni0.85Se-NHCS electrode has excellent discharging-charging performance and long lifetime. This work provides a valuable understanding on transition metal non-oxide electrocatalysts and expands the applications of selenide-based materials.