AbstractMost simple magnesium salts tend to passivate the Mg metal surface too quickly to function as electrolytes for Mg batteries. In the present work, an electroactive salt [Mg(THF)₆][AlCl₄]₂ was synthesized and structurally characterized. The Mg electrolyte based on this simple mononuclear salt showed a high Mg cycling efficiency, good anodic stability (2.5 V vs. Mg), and high ionic conductivity (8.5 mS cm⁻¹). Magnesium/sulfur cells employing the as‐prepared electrolyte exhibited good cycling performance over 20 cycles in the range of 0.3–2.6 V, thus indicating an electrochemically reversible conversion of S to MgS without severe passivation of the Mg metal electrode surface.