Electrocatalytic hydrogen peroxide (H₂O₂) production via the two-electron oxygen reduction reaction is a promising alternative to the energy-intensive and high-pollution anthraquinone oxidation process. However, developing advanced electrocatalysts with high H₂O₂ yield, selectivity, and durability is still challenging, because of the limited quantity and easy passivation of active sites on typical metal-containing catalysts, especially for the state-of-the-art single-atom ones. To address this, we report a graphene/mesoporous carbon composite for high-rate and high-efficiency 2e⁻ oxygen reduction catalysis. The coordination of pyrrolic-N sites -modulates the adsorption configuration of the *OOH species to provide a kinetically favorable pathway for H₂O₂ production. Consequently, the H₂O₂ yield approaches 30 mol g⁻¹ h⁻¹ with a Faradaic efficiency of 80% and excellent durability, yielding a high H₂O₂ concentration of 7.2 g L⁻¹. This strategy of manipulating the adsorption configuration of reactants with multiple non-metal active sites provides a strategy to design efficient and durable metal-free electrocatalyst for 2e⁻ oxygen reduction.

Electrochemical nitrogen reduction reaction (NRR) over nonprecious‐metal and single‐atom catalysts has received increasing attention as a sustainable strategy to synthesize ammonia. However, the atomic‐scale regulation of such active sites for NRR catalysis remains challenging because of the large distance between them, which significantly weakens their cooperation. Herein, the utilization of regular surface cavities with unique microenvironment on graphitic carbon nitride as “subnano reactors” to precisely confine multiple Fe and Cu atoms for NRR electrocatalysis is reported. The synergy of Fe and Cu atoms in such confined subnano space provides significantly enhanced NRR performance, with nearly doubles ammonia yield and 54%‐increased Faradic efficiency up to 34%, comparing with the single‐metal counterparts. First principle simulation reveals this synergistic effect originates from the unique Fe–Cu coordination, which effectively modifies the N₂ absorption, improves electron transfer, and offers extra redox couples for NRR. This work thus provides new strategies of manipulating catalysts active centers at the sub‐nanometer scale.