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Abstract Synthesis of metal-free carbon-based electrocatalysts for oxygen reduction reaction (ORR) to replace the conventional platinum-based catalysts has currently become a hot topic of research. This work proposes an activation-assisted carbonization strategy for the fabrication of nitrogen-doped nanoporous carbon microfibers (Me-CFZ-900) with a high BET surface area (~ 929.4 m2 g−1) via using melamine as a promoter/nitrogen source and bamboo-carbon biowastes as the carbon source with the help of a zinc chloride activator. Electrochemical tests showed that the Me-CFZ-900 material has exhibited excellent ORR electrocatalytic activity and long-term stability, and also displayed a quasi-four-electron ORR pathway in alkaline electrolyte. We also find that the graphitic-N may be the catalytically active site for the ORR, but the formation of planar-N can further help to promote the ORR activity for our catalysts. The results open a new space and provide a new idea to prepare valuable porous nanocarbon materials on the basis of carbonaceous solid wastes for catalysis of a wide range of electrochemical reactions in the future.