In situ Raman microscopy was used to study polysulfide speciation in the bulk ether electrolyte during the discharge and charge of a Li-S electrochemical cell to assess the complex interplay between chemical and electrochemical reactions in solution. During discharge, long chain polysulfides and the S-3(-) radical appear in the electrolyte at 2.4 V indicating a rapid equilibrium of the dissociation reaction to form S-3(-). When charging, however, an increase in the concentration of all polysulfide species was observed. This highlights the importance of the electrolyte to sulfur ratio and suggests a loss in the useful sulfur inventory from the cathode to the electrolyte. (C) The Author(s) 2018. Published by ECS.