Thiuram disulfide undergoes Cu(I)-catalyzed C-S cross-coupling with aryl iodides via Cu(OAc)2.H2O-assisted desulfurization to produce the S-thiocarbamate ester compounds efficiently. Various aryl iodides containing different substituents undergo smooth reaction with a series of cyclic and acyclic secondary amine based thiuram disulfides under open air atmosphere. A probable mechanistic pathway has been suggested based on control experiments and reported literature.