Two-electron oxygen reduction reaction (2e− ORR) for H2O2 production is regarded as a more ecologically friendly substitute to the anthraquinone method. However, the search of selective and cheap catalysts is still challenging. Herein, we developed a neutral-selective and efficient nonprecious electrocatalyst that was prepared from a commercial activated carbon (AC) by simply microwave-assisted ash impurity elimination and hydrogen peroxide oxidation for surface functional sites optimization. The oxygen configuration can be tuned with enriching carboxyl group up to 6.65 at.% by the dosage of hydrogen peroxide (mass ratio of H2O2/C = ∼0–8.3). Chemical titration experiments identified the carbonyl groups as the most potential active sites, with selectivity boosted by the additional carboxyl groups. The microwave-assisted moderate-oxidized activated carbon (MW-AC5.0) demonstrated optimal 2e− ORR activity and selectivity in neutral electrolyte (0.1 M K2SO4), with H2O2 selectivity reaching ∼75%–97%, a maximum H2O2 production rate (1.90 mol·gcatal −1·h−1@0.1 V) and satisfying faradaic efficiency (∼85%) in gas-diffusion-electrode. When coupled with Fenton reaction, it can degrade a model organic pollutant (methylene blue [MB], 50 ppm) to colorless in a short time of 20 min, indicating the potential applications in the environmental remediation.