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The lithium-sulfur battery is a compelling energy storage system because its high theoretical energy density exceeds Li-ion batteries at much lower cost, but applications are thwarted by capacity decay caused by the polysulfide shuttle. Here, proof of concept and the critical metrics of a strategy to entrap polysulfides within the sulfur cathode by their reaction to form a surface-bound active redox mediator are demonstrated. It is shown through a combination of surface spectroscopy and cyclic voltammetry studies that only materials with redox potentials in a targeted window react with polysulfides to form active surface-bound polythionate species. These species are directly correlated to superior Li-S cell performance by electrochemical studies of high surface area oxide cathodes with redox potentials below, above, and within this window. Optimized Li-S cells yield a very low fade rate of 0.048% per cycle. The insight gained into the fundamental surface mechanism and its correlation to the stability of the electrochemical cell provides a bridge between mechanistic understanding and battery performance essential for the design of high performance Li-S cells.