Oligothioethers 4-RC6H4 (SC6H4-4) nX (n= 1–3; X= Br, I; R= NO2; X= Br; R= MeO. n= 1 and 2; X= I; R= MeO. n= 4; X= Br; R= NO2) have been prepared through a process involving (i) palladium-catalyzed C–S coupling between 4-RC6H4 (SC6H4-4) n− 1I and 4-BrC6H4SH to give 4-RC6H4 (SC6H4-4) nBr and (ii) copper-catalyzed replacement of Br by I.