Real-time in situ spectroelectrochemical studies have been carried out in N,NЈ-dimethyl formamide containing lithium trifluoromethane sulfonate as an electrolyte and the results are reported. The results indicate that the primary reduction product of the cyclic form of sulfur, S 8c 2Ϫ , undergoes an equilibrium reaction to its linear chain counterpart, S 8l 2Ϫ , which then dissociates into various products. These two dianions and S 3 Ϫ• were produced along with a minor product, S 4 2Ϫ , at the potential corresponding to the first electron transfer. These products were further reduced or dissociated to species including S 7 2Ϫ , S 6 2Ϫ , S 5 2Ϫ , S 4 2Ϫ , S 3 2Ϫ , S 2 2Ϫ , and S 2Ϫ at the second electron-transfer step as evidenced by the spectral shifts observed during electrolysis. The reduction reactions are generally chemically reversible, making it possible to use sulfur reduction as a cathode reaction for Li/S batteries.