<p>Realizing practical lithium–sulfur batteries with high energy density requires lean electrolyte design. However, under low electrolyte/sulfur (<i>E/S</i>) ratios, highly concentrated lithium polysulfides in the electrolyte phase limit cycling and capacity. Here, we report that a small amount of Lewis acidic calcium cation in the electrolyte addresses the problems of lean electrolyte lithium–sulfur batteries. Because of its Lewis acidity, Ca²⁺ readily converts lithium polysulfides into CaS and S₈, preventing electrolyte jamming, polysulfide shuttle and Li corrosion. The in situ-formed CaS catalyzes the reduction reaction of lithium polysulfides. Ca²⁺ rejuvenates via electrochemical oxidation of CaS during charging, enabling a sustainable interconversion between Ca²⁺ and CaS during cycling. Li-S pouch cells with Ca²⁺ additive delivered an energy density of 493 Wh kg⁻¹ (<i>E/S</i> of 2.4 μL mg⁻¹) based on the total mass of the cell excluding external packaging, with 70% capacity retention at 220 cycle under 1 mA cm⁻² discharge, and 346 Wh kg⁻¹ (2.9 μL mg⁻¹) with 77% capacity retention at 360 cycle under 1.0 C 2 mA cm⁻² discharge. The judicious integration of lithium-sulfur and calcium-sulfur chemistries offers a handy but effective approach to overcome the long-lasting trade-off between energy density and cycling stability in the development of lithium–sulfur batteries.</p>