The polysulfide ions formed during the first reduction wave of sulfur in Li-S battery were determined through both in-situ and ex-situ derivatization of polysulfides. By comparing the cyclic voltammetric results with and without the derivatization reagent (methyl triflate) as well as the in-situ and ex-situ derivatization results under potentiostatic condition, in-situ derivatization was found to be more appropriate than its ex-situ counterpart, since subsequent fast chemical reactions between the polysulfides and sulfur may occur during the timeframe of ex-situ procedures. It was found that the major polysulfide ions formed at the first reduction wave of elemental sulfur were the S-4(2-) and S-5(2-) species, while the widely accepted reduction products of S-8(2-) and S-6(2-) for the first reduction wave were in low abundance. (C) 2015 Elsevier B.V. All rights reserved.