context: Increasing the areal sulfur loading and decreasing the amount of electrolyte in cathodes are natural methods to meet the above requirements. However, thick sulfur electrodes suffer cracking and peeling off problems during slurry casting, thus damaging the electrode integrity. Another obstacle for thick electrodes is the poor immersion of the electrolyte, which restrains the effective sulfur utilization. A promising alternate approach is to use a polysulfide solution, designated as a catholyte, as the starting material. The liquid catholyte is ready to immerse and envelope the surface of the conductive host, thus facilitating rapid charge transfer at the electrode/electrolyte interface, and giving rise to fast reaction kinetics. In addition, highly concentrated catholytes possess an intrinsically low E/S ratio. For example, the E/S ratio of 1.5 M Li2S6 catholyte is only 3.5 μL mg−1, which is difficult to achieve in sulfur particle electrodes. However, the flooded amounts of LPSs in carbon/catholyte electrodes induce a severe shuttling effect due to the poor interaction between the nonpolar carbon host and polar LPSs, leading to a short cycle life. Thus, introducing polar electrocatalysts in carbon/catholyte becomes imperative.