Integrating　selective　organic　synthesis　with　hydrogen　(H2)　evolution　in　one　photocatalytic　redox　reaction　system　sheds　light　on　the　underlying　approach　for　concurrent　employment　of　photogenerated　electrons　and　holes　towards　efficient　production　of　solar　fuels　and　chemicals.　In　this　work,　a　facile　one-pot　oil　bath　method　has　been　proposed　to　fabricate　a　noble　metal-free　ultrathin　Ni-doped　ZnIn2S4　(ZIS/Ni)　composite　nanosheet　for　effective　solar-driven　selective　dehydrocoupling　of　benzyl　alcohol　into　value-added　C–C　coupled　hydrobenzoin　and　H2　fuel,　which　exhibits　higher　performance　than　pure　ZIS　nanosheet.　The　remarkably　improved　photoredox　activity　of　ZIS/Ni　is　mainly　attributed　to　the　optimized　electron　structure　featuring　narrower　band　gap　and　suitable　energy　band　position,　which　facilitates　the　ability　of　light　harvesting　and　photoexcited　charge　carrier　separation　and　transfer.　Furthermore,　it　has　been　demonstrated　that　it　is　feasible　to　employ　ZIS/Ni　for　various　aromatic　alcohols　dehydrocoupling　to　the　corresponding　C–C　coupled　products.　It　is　expected　that　this　work　can　stimulate　further　interest　on　the　establishment　of　innovative　photocatalytic　redox　platform　coupling　clean　solar　fuels　synthesis　and　selective　organic　conversion　in　a　sustainable　manner.　©　2022　Dalian　Institute　of　Chemical　Physics,　the　Chinese　Academy　of　Sciences