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Carbon materials based catalysts (CMCs) are extensively investigated to replace expensive noble metal catalysts (NMCs) for electrochemical oxygen reduction reaction (ORR). However, two issues are needed to be clarified for further development: ORR on CMCs produces more H2O2 via 2e– process than that for NMCs in acidic condition, and the active sites for ORR of CMCs are still under debate. H2O2 formation on NMCs was thought to be activated by O2 adsorption on metal surfaces. Contrarily, the results of present study indicate that an O2 molecule would approach the hydrogen site on CMCs to form an OOH– ion which subsequently reacts with H+ to form a H2O2. The calculated electrochemical potentials, kinetics, and X-ray photoelectron spectroscopy (XPS) binding energy support well the new mechanism. Moreover, we found that the active sites for ORR are actually dependent on specific ORR process and the working potential range. The present work provides important insights into ORR for electrochemical devices.