The electro-oxidation of sulfur in polar organic media is reported at room temperature, the first such report under these conditions. Electroanalytical techniques such as current-potential curves, coulometry, and mirage effect demonstrated the formation of an electrophilic species S2+ (consumption of sixteen moles of electrons per mole of S8). At room temperature S2+ appears sufficiently stable in solution to be used as a reagent to prepare thio-organic compounds in the presence of nucleophiles.