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.