The　construction　of　C-S　bonds　is　very　important.　The　hydrothiolation　of　alkenes　or　alkynes　with　thiols　represents　an　attractive　and　atom　economical　approach　for　the　formation　of　C-S　bonds.　In　this　manuscript,　flowerlike　microspheres　of　ZnIn2S4　consisting　of　interweaving　nanoflakes　were　prepared　by　a　solvothermal　method　and　were　applied　for　the　first　time　in　the　visible　light　initiated　hydrothiolation　of　alkenes　and　alkynes.　The　reactions　between　a　broad　range　of　thiols　and　alkynes　or　alkenes　over　irradiated　ZnIn2S4　afford　the　corresponding　hydrothiolated　products　in　moderate　to　excellent　yields.　The　mechanism　proposed　based　on　the　ESR　results　suggests　that　the　holes　generated　over　irradiated　ZnIn2S4　are　reductively　quenched　by　the　thiols　to　generate　thiyl　radicals,　which　are　added　to　the　alkynes/alkenes　to　generate　alkene/alkyl　radicals　for　the　propagation　of　thiol-ene/thiol-yne　coupling　reactions.　The　use　of　solar　light　and　a　semiconductor-based　photocatalyst　to　realize　the　thiol-ene　and　thiol-yne　coupling　reactions　in　a　green　solvent　(methanol),　with　only　stoichiometric　thiols　required　and　applicable　to　a　broad　substrate　scope,　makes　this　reaction　protocol　a　green,　sustainable　and　cost-effective　strategy　for　the　synthesis　of　thiolated　products.　This　study　also　highlights　the　great　potential　of　semiconductor-based　photocatalysis　for　advanced　organic　syntheses.　©　2019　The　Royal　Society　of　Chemistry.