Some symmetric disulfides have been astonishingly prepared from thiophthalimides (sulfenimides) and amines in the presence of 2-ethoxyethanol (β-ee, neat) at microwave irradiation under free catalyst and ligand. The products were obtained in good to excellent yields ranging from 62% to 92%. When only thiophthalimides were exposed to microwave irradiation, disulfides were not obtained. Also, disulfides were not obtained from thiophthalimides in the presence of 2-ethoxyethanol (neat) under microwave irradiation. We compared the microwave-assisted synthesis method with the classical method. The products obtained were purified with chromatographic method and the analysis of them was performed with IR, 1H NMR, 13C NMR spectroscopic and elemental methods.