A new in operando spectro-electrochemical Li-S cell has been demonstrated. The novel design allows investigations of the liquid electrolyte phase, in a commercial coin cell geometry, at C rates much higher than conventional in situ cells. We use ATR FT-IR spectroscopy, coupled with a previously developed polysulfide diagnostic to quantify the evolution of lithium polysulfides during the discharge and charge cycles of a Li-S cell. The trends observed in the polysulfide order and concentration with respect to state of charge are consistent with prevailing understanding of the electrochemical mechanisms of Li-S battery operation. During discharge, we observe the reduction of elemental sulfur to dissolved Li 2 S 8 polysulfides, and their cascading conversion to smaller polysulfides until insoluble species ( Li 2 S 2 and Li 2 S ) are formed. During cell charging, we observe the oxidation of insoluble polysulfides to larger, soluble polysulfides ( Li 2 S n , n > 3 ), and infer an eventual recovery of crystalline sulfur, from changes in polysulfides. Long-term evolution of polysulfides is observed over 7 discharge/charge cycles. Capacity fading is evident in the decay of polysulfide order and concentration at the same state of charge between cycles. Sulfur is not recovered by charging the cell in the latter cycles, and the active material is lost as solid Li 2 S .