The redox mechanism of polysulfides in nonaqueous solvents is examined, For that purpose, Li2S6 + DMF solutions have been investigated by using cyclic voltammetry and time-resolved spectroelectrochemical experiments coupling spectrophotometry and cyclic voltammetry. It is shown that the only redox couples involved in these solutions are S-n(-)/S-n(2-) with n = 3,4,6,8 and S-8c/S-8c(-) (c for cyclic). The experimental results are interpreted by the following mechanism:This mechanism has been simulated and adjusted to the experimental voltammograms in broad temperature (233 to 313 K) and scan rate (50 to 2000 mV/s) ranges, recorded for an initial scan in the positive direction and in the negative direction. We have obtained a complete description of the redox properties of sulfur and polysulfides in this solvent. We have shown that only the radical anions S-n(-) are reducible and that only the dianions S-n(2-) are oxidizable. It is also shown that this mechanism describes the two steps of the reduction mechanism of sulfur in DMF.