Two　atomic　layered　BiOCl　nanosheets　with　rich　oxygen　vacancies　(NS-OV)　were　constructed　via　surface　Pd　deposition　(0.5　wt%)　as　a　multifunctional　photocatalyst　(Pd-0.5/NS-OV),　which　exhibits　high　conversion　(＞　95%)　and　precise　selectivity　(＞　98%)　for　benzylamine　coupling　to　N-benzylidenebenzylamine　under　visible　light　irradiation　and　1　atm　air　pressure.　XPS　and　UV-vis　DRS　indicated　that　ultrathin　structure　of　the　nanosheets　induces　the　formation　of　surface　oxygen　vacancies　(OV),　resulting　in　abundant　surface　low-coordinated　Bi　atoms　and　expanded　visible　light　absorpion.　Moreover,　in-situ　EPR　results　revealed　that　surface　OV　sites　contribute　to　assemble　O-2　molecules　from　air　to　surface　of　NS-OV.　Additionally,　in-situ　FTIR　suggested　that　low-coordinated　Bi　selectively　adsorb　benzylamine　molecules　via　-N...Bi-coordination　bonds　at　the　interfaces,　inducing　polarization　and　activation　of-C-N　bonds.　Furthermore,　Pd　sites　were　observed　to　crucially　participate　in　formation　of　active　&　BULL;O-2(-)　species　under　visible　light　irradiation.　Based　on　multifunctional　features,　a　possible　synergistic　mechanism　was　proposed.