Surface-complex　functional　modification　is　a　promising　strategy　in　activating　TiO2　for　visible　light　harvesting.　However,　the　fundamental　nature　of　the　interfacial　microstructures　between　complex　and　TiO2,　and　how　they　affect　the　significant　interfacial　charge　transfer　process　remain　vague.　In　this　work,　a　facile　one-step　visible-light-driven　approach　has　been　developed　for　the　production　of　surface-complex　and　stable　defects　over　TiO2　surface　under　normal　ambient　conditions.　It　is　found　that　the　photo-deposition　of　2-naphthol　on　TiO2　can　trigger　a　reconstruction　of　TiO2　surface　to　form　a　interfacial　dyadic　structure,　which　consists　of　conductive　surface-complex　and　unique　interfacial　microstructures　(Ti-O-C　bonds　and　defects).　defects.　The　interfacial　defects　(Ti3+　and　oxygen　vacancies)　can　be　stabilized　by　the　surface-complex　coating,　and　introduce　defective　states　in　the　band　gap　of　TiO2.　This　unique　interfacial　dyadic　structure　can　effectively　promote　the　visible-light-driven　photoelectric　and　photocatalytic　performance.　A　corresponding　mechanism　is　also　proposed　to　elucidate　the　formation　of　this　unique　interfacial　dyadic　structure,　and　reveal　its　synergistic　effect　on　the　interfacial　charge　transfer　behavior.　This　work　contributes　fundamentally　to　not　only　the　mechanism　studies,　but　also　the　rational　design　of　novel　and　high-efficiency　photocatalysts　with　high　visible　light　harvesting.