<p>The practical deployment of lithium–sulfur batteries (LSBs) is fundamentally limited by the sluggish stepwise sulfur redox kinetics. However, current design philosophies remain heavily constrained by the conventional “adsorption-catalysis” strategy, often overlooking the crucial rate-limiting kinetic obstacle of the high Li⁺ desolvation energy barrier. This sluggish Li⁺ desolvation process imposes a severe kinetic penalty on polysulfide conversion, thereby depressing electrochemical stability. Herein, we propose a catalyst desolvation strategy utilizing a Ce single-atom catalyst to promote the Li⁺ desolvation process, thereby enhancing the redox conversion of polysulfides. Results indicate that the catalyst desolvation strategy increases the proportion of contact ion pairs and aggregates, reduces the Li⁺ desolvation energy barrier, and stabilizes the lithium anode/electrolyte interface. Consequently, the accelerated Li⁺ desolvation facilitates rapid sulfur redox kinetics, thereby realizing stable cycling in LSBs with a low decay rate of 0.036% per cycle over 1700 cycles at 1 C. This work confirms the significant impact of Li⁺ desolvation and provides a new solution for achieving efficient conversion of polysulfides in LSBs.</p>