Close　proximity　between　different　catalytic　sites　is　crucial　for　accelerating　or　even　enabling　many　important　catalytic　reactions.　Photooxidation　and　photoreduction　in　photocatalysis　are　generally　separated　from　each　other,　which　arises　from　the　hole-electron　separation　on　photocatalyst　surface.　Here,　we　show　with　widely　studied　photocatalyst　Pt/TiO2　as　a　model,　that　concentrating　abundant　oxygen　vacancies　only　at　the　metal-oxide　interface　can　locate　hole-driven　oxidation　sites　in　proximity　to　electron-driven　reduction　sites　for　triggering　unusual　reactions.　Solar　hydrogen　production　from　aqueous-phase　alcohols,　whose　hydrogen　yield　per　photon　is　theoretically　limited　below　0.5　through　conventional　reactions,　achieves　an　ultrahigh　hydrogen　yield　per　photon　of　1.28　through　the　unusual　reactions.　We　demonstrated　that　such　defect　engineering　enables　hole-driven　CO　oxidation　at　the　Pt-TiO2　interface　to　occur,　which　opens　up　room-temperature　alcohol　decomposition　on　Pt　nanoparticles　to　H-2　and　adsorbed　CO,　accompanying　with　electron-driven　proton　reduction　on　Pt　to　H-2.