AbstractOxygen reduction reaction towards hydrogen peroxide (H₂O₂) provides a green alternative route for H₂O₂ production, but it lacks efficient catalysts to achieve high selectivity and activity simultaneously under industrial-relevant production rates. Here we report a boron-doped carbon (B-C) catalyst which can overcome this activity-selectivity dilemma. Compared to the state-of-the-art oxidized carbon catalyst, B-C catalyst presents enhanced activity (saving more than 210 mV overpotential) under industrial-relevant currents (up to 300 mA cm⁻²) while maintaining high H₂O₂ selectivity (85–90%). Density-functional theory calculations reveal that the boron dopant site is responsible for high H₂O₂ activity and selectivity due to low thermodynamic and kinetic barriers. Employed in our porous solid electrolyte reactor, the B-C catalyst demonstrates a direct and continuous generation of pure H₂O₂ solutions with high selectivity (up to 95%) and high H₂O₂ partial currents (up to ~400 mA cm⁻²), illustrating the catalyst’s great potential for practical applications in the future.