Carbamo(dithioperoxo)thioate compounds have been synthesized in aqueous medium under open aerial condition at room temperature. N‐(Arylthio)phthalimides are used as electrophilic sulfur donors which react with in situ generated dithiocarbamate anions to produce carbamo(dithioperoxo)thioates in excellent yields. After the reaction, phthalimide residue was recovered and reused to prepare N‐(Arylthio)phthalimides.