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The oxygen evolution reaction (OER) is an important half-reaction in electrochemical hydrogen production (EHP) and rechargeable meta-air batteries. However, the sluggish OER kinetics has seriously impeded the performance. Herein, we report a bioelectrochemical cascade system composed of glucose oxidase (GOx)-functionalized N-doped porous carbon nanofibers to replace OER in EHP and rechargeable Zn-air batteries (ZABs) applications.