The　oxygen　reduction　reaction　(ORR)　can　proceed　through　either　a　two-　or　four-electron　pathway,　both　of　which　are　important　for　a　wide　range　of　applications.　The　intermediate　conversion　of　*O2⁻　+　H⁺　→　*OOH　recognized　as　the　rate-determining　step　in　ORR,　with　its　efficiency　strongly　dependent　on　the　nature　of　active　sites　at　the　surface　of　a　catalyst.　Herein,　Si-supported　carbon　dots　(Si-CDs)　are　introduced　as　cocatalysts　in　a　photocatalytic　system,　where　their　nitrogen–carbon　sites　play　a　pivotal　role　in　lowering　the　energy　barrier　for　*OOH　formation　by　promoting　proton　and　electron　transfers,　thus　enhancing　the　H2O2　production　rate　in　ORR.　This　strategy　is　broadly　applicable　across　a　wide　range　of　photocatalysts,　both　with　and　without　use　of　sacrificial　agents.　The　H2O2　production　rate　for　Zn0.5Cd0.5S　(30 mg)　increased　from　13.0　to　40.9 µmol　h−1　when　0.6 mg　of　Si-CDs　were　added.　In-situ　characterizations　and　theoretical　simulations　are　conducted　to　reveal　the　reaction　pathway　and　the　reduced　energy　requirements　for　the　*O2⁻　+　H⁺　→　*OOH　conversion.　This　study　provides　a　unique　example　of　overcoming　a　key　barrier　in　ORR　using　a　metal-free　catalyst　and　promotes　potential　applications　in　various　fields.　©　2025　Wiley-VCH　GmbH.