The reduction of sulfur in an aprotic solvent (DMSO) is known to be a two‐stage process; each stage involves a bielectronic electrochemical step followed by a chemical dismutation reaction. When reduction is performed at a rotating electrode, it is shown that the electrochemical steps alone are involved in the electrode process. The voltammetric waves then correspond to the simple scheme The slower dismutation reactions appear only in the bulk of solution. They lead to electron numbers which differ from 2 when is electrolyzed. The addition of Cd2+ ions to a polysulfide ion solution yields soluble polysulfide‐cadmium 2:1 complexes with . The stability of the complex is increased when decreases from 8 to 4, which leads to dismutation and exchange reactions between complexes, polysulfide ions, and sulfur.