Abstract Hydrogen peroxide, as a green oxidant, received broad and increasing applications. Membrane technology affords a promising solution to achieve in-situ production and concentration of hydrogen peroxide. Membrane material selection and structure design remain a grand challenge arising from the strong oxidation property of hydrogen peroxide. Herein, we explored graphene oxide membranes to concentrate hydrogen peroxide for the first time. By manipulating the cross-linking process of thiourea molecules, the interlayer channel size can be tuned in the range of 2.9–3.2 A, ensuring the distinct molecular sieving between water and hydrogen peroxide. The graphene oxide membranes displayed superior separation performance with separation factor of 22.8 and permeation flux of 18.2 kg m−2 h−1. Compared with conventionally water-permeable membranes, graphene oxide membranes exhibit excellent antioxidative ability and stability in the 168 h operation test.