<p>Magnesium–sulfur batteries offer high theoretical energy density but suffer from low sulfur utilization and rapid capacity fading. This work identifies the strong Mg²⁺–polysulfide Coulombic interaction as responsible for sluggish kinetics. We demonstrate that the solvation of magnesium polysulfides fundamentally governs their behavior, relaxing Mg²⁺–polysulfide coupling to facilitate polysulfide speciation and conversion kinetics. Our findings reveal that solvation with high shielding ability effectively modifies the binding configuration of magnesium polysulfides, which lowers the energy barrier for their stepwise conversion, thus improving reaction reversibility. Furthermore, under solvation modulation, magnesium sulfide deposition exhibits a three-dimensional nucleation morphology, providing more active sites for redox. Consequently, the developed cells achieve the equilibrium potential ~1.1 V (vs. Mg/Mg²⁺) and extended cycle life (0.1 C over 120 cycles,1 C (60 min) = 1675 mA g^-1), with pouch cells showing high discharge capacity (940.80 mAh g⁻¹ in the 1^st cycle; &gt; 600 mAh g^-1 after 18 cycles).</p>