Owing　to　the　simultaneous　utilization　of　photogenerated　electrons　and　holes,　coupling　light-driven　hydrogen　(H2)　evolution　reaction　(HER)　and　biomass-derived　alcohol　conversion　reactions　in　one　photoredox　cycle　has　aroused　many　interests　for　the　coproduction　of　valuable　chemical　products　and　renewable　fuels.　In　this　study,　a　facile　photochemical　reduction　approach　has　been　used　to　decorate　MoS2　cocatalyst　on　ZnIn2S4　nanoflowers　(NFs)　for　photocatalytic　coupling　reactions　of　selective　benzyl　alcohol　(BA)　oxidation　and　HER.　The　results　reveal　that　1%MoS2/ZnIn2S4　composite　photocatalyst　displays　the　best　visible-light-induced　photoactivity　for　BA　conversion　(3.69 mmol g−1 h−1)　and　H2　evolution　(3.88 mmol g−1 h−1),　exhibiting　6　times　as　high　as　the　photoactivity　over　bare　ZnIn2S4.　The　MoS2　cocatalyst　markedly　improves　charge　separation　and　mitigates　the　overpotential　of　HER,　thereby　accelerating　H2　production　kinetics　for　the　coproduction　reactions.　The　photoreduction　of　Cr　(VI)　and　4-nitroaniline　(4-NA)　is　also　investigated　to　verify　the　universality　of　MoS2　as　high-performance　cocatalyst.　The　carbon-centered　radical　is　identified　in　BA　conversion　over　MoS2/ZnIn2S4　composite　photocatalyst.　This　work　could　contribute　to　the　rational　construction　of　ZnIn2S4-based　cooperative　photoredox-catalyzed　system　toward　efficient　coproduction　of　value-added　fine　chemicals　and　clean　fuels.　Graphical　abstract:　[Figure　not　available:　see　fulltext.]　©　2021,　The　Author(s),　under　exclusive　licence　to　Springer　Nature　B.V.