Exploring highly effective and low-cost non-noble metal-based electrocatalysts for oxygen evolution reaction (OER) is critical for renewable energy conversion and metal-air batteries. Herein, a novel and high-efficient OER catalyst was reported with nitrogen-doped oxide/sulfide heterostructures (named N-NiCo2S4/CoO microsphere). The N-NiCo2S4/CoO microsphere was synthesized by annealing NiCo-BTC MOF to a multi-layered hollow structure of NiCo2O4 microspheres, followed by the direct vulcanization in the presence of NH4HCO3, resulting in an oxide/sulfide heterojunction. Benefiting from the nitrogen doping, the abundant multi-layered hollow heterostructure and the interfaces between multiple components, the N-NiCo2S4/CoO microsphere exhibited excellent OER activity with a low overpotential of 227 mV at 10 mA cm-2. The Zn-air battery based on the N-NiCo2S4/CoO + Pt/C catalyst displayed excellent cycling stability after 900 cycles at a large current density of 5 mA cm-2, where the commercial RuO2 + Pt/C-based battery exhibited a big drop after only 30 cycles, suggesting its great application prospects as power source devices.