Designing　efficient　metal　organic　frameworks　(MOF)-based　photocatalysts　has　recently　attracted　wide　attention.　In　this　work,　Au　nanoparticles(NPs)-decorated　defective　DUT-67(Zr)　(Au@DUT-67(Zr))　with　enlarged　channels　was　successfully　fabricated　and　achieved　7.5　times　higher　conversion　than　Au　NPs-decorated　UiO-66(Zr)　(Au@UiO-66(Zr))　for　photocatalytic　selective　oxidation　of　amines　to　imines　driven　by　visible　light.　Au　NPs　are　more　effectively　fixed　on　DUT-67(Zr)　due　to　its　partially　hollow　structure.　Au@DUT-67(Zr)　possesses　more　active　sites　including　unsaturated　Zr　atoms　and　oxygen　vacancies　(VO)　than　Au@UiO-66(Zr).　In　situ　Fourier　transform　infrared　(FTIR)　spectrum　reveals　that　benzylamine　is　activated　on　unsaturated　Zr　sites　via　H[sbnd]N…Zr　species,　facilitating　deprotonation　of　–CH2　in　benzylamine.　VO　can　not　only　adsorb　and　activate　oxygen　(O2)　but　also　capture　plasmonic　hot　electrons,　enhancing　the　forming　of　superoxide　radical　([rad]O2−).　Plasmonic　hot　holes　assisted　with　[rad]O2−　effectively　achieve　the　selective　oxidation　of　benzylamine.　Finally,　a　possible　synergetic　mechanism　combining　the　plasmon　with　the　molecular　activation　is　presented　to　illustrate　the　photocatalytic　pathway　at　the　molecular　level.　©　2022　Elsevier　Inc.