A　highly　porous　metal-organic　framework　based　on　supramolecular　building　blocks　with　pcu-topology　(pcu-MOF)　has　been　tested　for　the　oxidative　coupling　of　amines　and　disulfides　or　thiols　to　afford　the　N-sulfenylimines　directly　in　good　yields　without　the　formation　of　N-sulfinyl-　and　N-sulfonylimines.　The　pcu-MOF　catalyst　could　be　easily　recovered　from　the　reaction　mixture　by　simple　filtration,　and　could　be　reused　at　least　five　times　without　any　substantial　loss　in　the　yield.　The　control　experiments　and　mechanistic　studies　suggested　that　the　oxidative　coupling　process　involved　the　imine　formation　and　the　N-S　coupling　reaction.