H2O2 is an important chemical widely used in paper, textile, water treatment and other fields, while the current industrial anthraquinone pathway is not sustainable. Herein, a highly efficient electrocatalyst, reduced graphene oxide (rGO-KOH), applied for electrochemical H2O2 production was obtained by treating graphene oxide (GO) with KOH aqueous solution. Compared to KBH4-treated reduced graphene oxide (rGO-KBH4) made by KBH4 reduction method, rGO-KOH has more ether bonds (C–O–C) on the surface and a larger electrochemically active surface area. Benefiting from these advantages, rGO-KOH exhibits enhanced selectivity (∼100%) and mass activity for the oxygen reduction reaction through a two-electron pathway (ORR-2e) than rGO-KBH4. Meanwhile, rGO-KOH also shows the excellent durablity for (ORR-2e) in alkaline media. Thus, rGO-KOH may be an ideal electrocatalyst for H2O2 electroproduction.