The metal-free carbon-based catalyst with low cost and high oxygen reduction reaction (ORR) activity is urgently desired to satisfy the demands of microbial fuel cells (MFCs). However, it is still a great challenge to develop a facile and feasible strategy to construct efficient active sites of heteroatom doping for carbon-based electrocatalyst. Herein, we report a strategy based on an ammonium fluoride (NH4F) gas-steamed metal-organic frameworks (MOFs) to heighten structural defects and density of N, F active sites of metal-free catalyst. Oxygen temperature-programmed deposition and density functional theory results confirm that the NH4F gas-steamed process greatly enhances the adsorption affinity of O2 and oxygen intermediates on the catalysts. The resulted N and F co-doped porous carbon cage (FNC-15) demonstrates outstanding ORR catalytic activity and long-term stability in alkaline and neutral electrolytes. This work proposes a facile and efficient in situ gas-steamed strategy to develop metal-free cathode catalysts with superior performance.