Electrochemical H2O2 production via oxygen reduction reaction (ORR) with 2e− pathway is suitable for continuous on-site production. In this regard, it is important to develop catalysts showing high activity and selectivity for 2e− pathway ORR. Carbon nanomaterials have been investigated as a class of highly promising catalysts for H2O2 production. To identify the critical design factor for highly active H2O2 production electrocatalysts, we prepared graphitic ordered mesoporous carbon (GOMC) model catalysts with controlled ratios of edge to basal length. We found that there is a positive correlation between activity of the H2O2 production and the edge to basal ratio. Furthermore, acid treated-GOMC (O-GOMC) catalysts further boosted catalytic activity, compared to GOMC catalysts. Notably, our most active catalyst (O-GOMC-75) showed the best H2O2 production mass activity (120 A/g @ 0.7 V) among the reported carbon-based catalysts. Moreover, O-GOMC-75 exhibited excellent stability (168 h @ 3.09 mA) with 99.2% faradaic efficiency and 64.1 mg L−1 h−1 accumulation rate of the H2O2.