H2O2 is a potential energy carrier and an environmental-friendly oxidant, which is produced by anthraquinone method in industry. This multistep batch method is energy intensive and difficult for in-situ H2O2 synthesis. Electrosynthesis of H2O2 from O2 Reduction is an attractive alternative method, which enables in situ H2O2 production at room temperature and atmospheric pressure. However, developing active and cost-effective electrocatalyst which selectively reduces O2 to H2O2 (two-electron pathway) over H2O remains great challenge. Herein, hierarchically porous carbon (HPC) derived from MOF carbonization was designed for electrosynthesis of H2O2 from O2 reduction.