Defects　can　greatly　optimize　the　solar　light　harvesting　capability　and　electronic　structure　of　oxide　materials.　However,　it　remains　challenging　to　achieve　a　defect　engineering　strategy　under　mild　conditions.　Meanwhile,　the　simultaneous　exploitation　of　photogenerated　holes　(h+)　and　electrons　(e−)　to　promote　both　photooxidation　and　photoreduction　in　a　coupled　system　has　rarely　been　reported.　For　the　first　time,　we　reveal　an　oxygen-vacancies-mediated　photocatalytic　strategy　in　which　the　electrons　and　holes　are　fully　utilized　for　nitrobenzene　reduction　coupled　with　benzyl　alcohol　oxidation.　The　oxygen　vacancies　(OVs)　generated　in　situ　on　the　surface　of　TiO2　greatly　extend　light　absorption　into　the　visible　region　and　promote　the　photogenerated　electron　transport　for　efficient　photocatalysis.　The　experimental　and　theoretical　results　together　indicate　that　chemisorption　on　the　TiO2　surface　decreases　the　oxidation　potential　of　benzyl　alcohol　and　causes　an　upward　shift　in　its　HOMO,　which　facilitates　the　oxidation　reaction　of　benzyl　alcohol　to　benzaldehyde.　The　in　situ　generated　surface　OVs　also　act　as　a　bridge　to　enable　the　trapping　and　transferring　of　the　photoinduced　electrons　to　the　nitrobenzene.　This　work　provides　a　new　perspective　of　utilizing　the　chemisorption　between　the　reactant　and　catalyst　to　achieve　a　defect　engineering　strategy　for　synergetic　photocatalysis.　©　2019