Copper-based　metal–organic　frameworks　(Cu-MOFs)　are　a　promising　multiphase　catalyst　for　catalyzing　C–S　coupling　reactions　by　virtue　of　their　diverse　structures　and　functions.　However,　the　unpleasant　odor　and　instability　of　the　organosulfur,　as　well　as　the　mass-transfer　resistance　that　exists　in　multiphase　catalysis,　have　often　limited　the　catalytic　application　of　Cu-MOFs　in　C–S　coupling　reactions.　In　this　paper,　a　Cu-MOFs　catalyst　modified　by　cetyltrimethylammonium　bromide　(CTAB)　was　designed　to　enhance　mass　transfer　by　increasing　the　adsorption　of　organic　substrates　using　the　long　alkanes　of　CTAB.　Concurrently,　elemental　sulfur　was　used　to　replace　organosulfur　to　achieve　a　highly　efficient　and　atom-economical　multicomponent　C–S　coupling　reaction.　©　2024　The　Chemical　Industry　and　Engineering　Society　of　China,　and　Chemical　Industry　Press　Co.,　Ltd