AbstractSemi‐liquid catholyte Lithium−Sulfur (Li−S) cells have shown to be a promising path to realize high energy density energy storage devices. In general, Li−S cells rely on the conversion of elemental sulfur to soluble polysulfide species. In the case of catholyte cells, the active material is added through polysulfide species dissolved in the electrolyte. Herein, we use operando Raman spectroscopy to track the speciation and migration of polysulfides in the catholyte to shed light on the processes taking place. Combined with ex‐situ surface and electrochemical analysis we show that the migration of polysulfides is central in order to maximize the performance in terms of capacity (active material utilization) as well as interphase stability on the Li‐metal anode during cycling. More specifically we show that using a catholyte where the polysulfides have the dual roles of active material and conducting species, e. g. no traditional Li‐salt (such as LiTFSI) is present, results in a higher mobility and faster migration of polysulfides. We also reveal how the formation of long chain polysulfides in the catholyte is delayed during charge as a result of rapid formation and migration of shorter chain species, beneficial for reaching higher capacities. However, the depletion of ionic species during the last stage of charge, due to the conversion to and precipitation of elemental sulfur on the cathode support, results in polarization of the cell before full conversion can be achieved.