Abstract Electrochemical reduction of molecular O2 to hydrogen peroxide (H2O2) offers a promising solution for water purification and environmental remediation. Here, we design a hierarchical free‐standing single‐Co‐atom (with Co–N4 coordination) electrode for oxygen reduction reaction (ORR) via a two‐electron pathway to make H2O2 in acidic media. The current density of the single‐Co‐atom electrode reached 51 mA/cm2 at 0.1 V vs reversible hydrogen electrode, lasting for more than 10 hours of continuous operation with H2O2 selectivity greater than 80%. Toward practical application, the single‐Co‐atom electrode was directly used to assemble an electrochemical cell to produce H2O2 at a rate of 676 mol/kgcat/h with a cell voltage of about 1.6 V.
