We discuss here various combinations of magnesium bis (hexamethyldisilazide) (Mg­(HMDS)2) with aluminum chloride (AlCl3) or magnesium chloride (MgCl2) in a solvent mixture of 1,3-dioxalane (DOL) and 1,2-dimethoxyethane (DME) (DOL/DME) as alternative electrolytes for practical rechargeable Mg–sulfur batteries. This design strategy is contrary to the usage of the solvents tetraglyme and tetrahydrofuran (THF) commonly used with Mg­(HMDS)2 to generate electrolyte formulations for Mg/S batteries. Cyclic voltammetry measurements reveal a higher current response for DOL/DME compared to tetraglyme and THF solvent-based electrolytes. Exemplary plating/stripping efficiency is obtained at room temperature and is observed to be strongly dependent on the salt concentrations. The remarkable stripping/plating reversibility (at a current density of 0.1 mA cm–2) in a Mg||Mg symmetric cell indicates the extraordinary compatibility of the electrolyte with the Mg anode. The plating of Mg on the gold working electrode is ascertained using X-ray diffraction and scanning electron microscopy. The versatility of the Mg­(HMDS)2-based electrolyte in the DOL/DME solvent is further utilized in a Mg/S cell with a simple carbon nanotube–sulfur composite as the cathode and Mg-metal as the anode. The DOL/DME-Mg­(HMDS)2 electrolyte-based Mg/S cell exhibited stable electrochemical performance over widely varying current densities ranging from 0.05 to 0.5 C.