Unsymmetrical and cyclic disulfides with thiophene units have been prepared. Electrochemical studies show the alteration of their behavior versus thiophene parents due to the second oxydation site. Polymerization of some of them leads to electroactive materials. A new efficient synthesis of the dithieno [3, 2-c: 2′, 3′-e][1, 2] dithiine is described.