Photocatalytic　oxygen　reduction　to　produce　hydrogen　peroxide　(H2O2)　is　a　promising　route　to　providing　oxidants　for　various　industrial　applications.　However,　the　lack　of　well-designed　photocatalysts　for　efficient　overall　H2O2　production　in　pure　water　has　impeded　ongoing　research　and　practical　thrusts.　Here　we　present　a　cyanide-based　covalent　organic　framework　(TBTN-COFs)　combining　2,4,6-trimethylbenzene-1,3,5-tricarbonitrile　(TBTN)　and　benzotrithiophene-2,5,8-tricarbaldehyde　(BTT)　building　blocks　with　water-affinity　and　charge-separation.　The　ultrafast　intramolecular　electron　transfer　(−1　g−1　yield　rate　of　H2O2　can　be　achieved　without　any　sacrificial　agent,　outperforming　most　previous　reports.　Furthermore,　the　DFT　calculation　and　in　situ　DRIFTS　spectrums　suggesting　a　Yeager-type　absorption　of　*O2⋅−　intermediate　in　the　cyanide　active　site,　which　prohibits　the　formation　of　superoxide　radical　and　revealing　a　favored　H2O2　production　pathway.　©　2024　Wiley-VCH　GmbH.