The　synergistic　of　organic　transformation　with　H2　production　in　one　redox　cycle　is　highly　desirable　to　achieve　the　full　use　of　photogenerated　holes　and　electrons　but　challenging.　Herein,　Lewis　acid-base　nanocatalysts　in　which　Ni　decorated　defective　ZnIn2S4　(denoted　as　Ni/VZIS)　has　been　prepared　through　photodeposition　with　Zn　defective　ZnIn2S4　nanosheets　as　precursor.　The　Zn　vacancies　favors　the　selective　deposition　of　Ni,　enabling　the　co-exposure　of　Lewis　acid　Ni　and　Lewis　base　S　adjacent　dual　active　sites.　In-situ　FTIR　results　reveal　the　coexistence　of　Ni　and　Zn　vacancy　on　ZnIn2S4　favored　the　chemisorption　of　benzyl　alcohol.　The　electron-deficient　Ni　Lewis　acid　(LA)　site　and　electron-rich　S　Lewis　base　(LB)　site　can　act　as　benzyl　alcohol　conversion　and　H2　evolution　sites,　respectively,　thus　facilitating　the　full　use　of　photoinduced　electrons　and　holes.　The　spectroscopy　and　photoelectrochemical　studies　demonstrate　the　transfer　and　separation　of　photogenerated　carries　are　also　facilitated　in　the　nanohybrids.　As　such,　the　Ni/VZIS　photocatalyst　show　outstanding　performance　of　photocatalytic　conversion　benzyl　alcohol　(BA)　into　benzaldehyde　(BAD)　and　H2,　with　the　optimal　H2　generation　rate　of　81.9　μmol　h−1,　accompanying　benzaldehyde　generation　rate　of　73.7　μmol　h−1.　This　work　provides　a　profound　insight　into　the　designing　of　multi-functionalized　nanohybrids　for　the　full　use　of　photoexcited　electrons-holes　pairs.　©　2023　Hydrogen　Energy　Publications　LLC