Enormous　efforts　have　been　devoted　to　exploring　the　influence　of　the　materials’　morphology　on　photocatalytic　performance,　while　the　role　of　active　site　between　them　attracts　less　attention.　Herein,　three　types　of　anatase　nano-TiO2　with　different　morphologies　were　successfully　prepared　for　visible-light-driven　photocatalytic　selective　oxidation　of　benzylamine.　The　material　properties　of　the　samples　were　systematically　studied　by　various　characterization　techniques　such　as　XRD,　SEM,　TEM,　AFM,　XPS,　UV–vis　DRS,　ESR　and　in　situ　FTIR.　Due　to　possessing　clear　advantages　especially　for　having　more　active　sites　(coordinatively　unsaturated　Ti　atoms　and　oxygen　vacancies),　the　TiO2　with　porous　structure　shows　more　excellent　photocatalytic　performance　than　the　other　samples.　Coordinatively　unsaturated　Ti　atoms　can　chemisorb　and　activate　benzylamine　molecules　via　forming　H-N…Ti　coordination　species,　whose　absorption　property　of　visible　light　guarantees　that　TiO2　samples　can　achieve　the　photocatalytic　process　under　visible　light.　Oxygen　vacancies　can　chemisorb　and　activate　oxygen　molecules　to　form　reactive　oxygen　species　(superoxide　radical)　by　the　reduction　of　photogenerated　electrons.　Finally,　a　possible　synergetic　mechanism　based　on　the　interaction　of　reactants　and　catalyst　interfaces　was　proposed　at　the　molecular　level　to　illustrate　the　photocatalytic　process.　©　2021　Elsevier　B.V.