A hierarchical carbon nanosheet array electrode with a single-atom Ni catalyst was developed for efficient electrochemical oxygen reduction to hydrogen peroxide (H₂O₂) under alkaline conditions. The electrode, synthesized using organic molecule-intercalated layered double hydroxides as precursors, exhibits excellent 2e⁻ ORR performance, achieving H₂O₂ yield rates of 0.73 mol g⁻¹ h⁻¹ in the H-cell and 5.48 mol g⁻¹ h⁻¹ in the flow cell, surpassing most reported catalysts. The Ni atoms selectively adsorb O₂, while carbon nanosheets generate reactive hydrogen species, synergistically enhancing H₂O₂ production. A coupling reaction system integrating the 2e⁻ ORR with ethylene glycol oxidation significantly enhances H₂O₂ yield rate to 7.30 mol g⁻¹ h⁻¹ while producing valuable glycolic acid. The system also converts alkaline electrolyte containing H₂O₂ directly into sodium perborate, reducing separation costs. Techno-economic analysis validates the economic viability of this system, with a profit margin of 15.65×10⁶ per year. The Ni-SAC electrode demonstrates strong *OOH adsorption, synergistically enhancing the 2e⁻ ORR performance. The system achieves a high H₂O₂ yield rate of 7.30 mol g⁻¹ h⁻¹ through the coupling of glycol oxidation. The electrolyte containing H₂O₂ can be directly converted to a downstream product, reducing separation costs. This work represents a promising and energy-saving design for the alkaline electrosynthesis of H₂O₂ with potential applications.A hierarchical carbon nanosheet array electrode with a single-atom Ni catalyst was developed for efficient electrochemical oxygen reduction to hydrogen peroxide (H₂O₂) under alkaline conditions. The electrode, synthesized using organic molecule-intercalated layered double hydroxides as precursors, exhibits excellent 2e⁻ ORR performance, achieving H₂O₂ yield rates of 0.73 mol g⁻¹ h⁻¹ in the H-cell and 5.48 mol g⁻¹ h⁻¹ in the flow cell, surpassing most reported catalysts. The Ni atoms selectively adsorb O₂, while carbon nanosheets generate reactive hydrogen species, synergistically enhancing H₂O₂ production. A coupling reaction system integrating the 2e⁻ ORR with ethylene glycol oxidation significantly enhances H₂O₂ yield rate to 7.30 mol g⁻¹ h⁻¹ while producing valuable glycolic acid. The system also converts alkaline electrolyte containing H₂O₂ directly into sodium perborate, reducing separation costs. Techno-economic analysis validates the economic viability of this system, with a profit margin of 15.65×10⁶ per year. The Ni-SAC electrode demonstrates strong *OOH adsorption, synergistically enhancing the 2e⁻ ORR performance. The system achieves a high H₂O₂ yield rate of 7.30 mol g⁻¹ h⁻¹ through the coupling of glycol oxidation. The electrolyte containing H₂O₂ can be directly converted to a downstream product, reducing separation costs. This work represents a promising and energy-saving design for the alkaline electrosynthesis of H₂O₂ with potential applications.