To realize a high-performance room temperature Na/S battery with an elemental sulfur cathode, it is important that sodium polysulfides stay within the cathode and that they have room enough to react freely. In this work, sodium polysulfides are confined to the cathode using a β″ alumina solid electrolyte separator and an optimal amount of tetraethylene glycol dimethyl ether (TEGDME) electrolyte. In addition, an activated carbon material, in the form of a sulfur/carbon (S/C) composite, with high surface area, porosity, and pore volume is employed in the cathode. The resulting Na/S battery shows a high first discharge capacity of 855 mAh g−1 and coulombic efficiency close to 100%, as well as stable cyclability, with a discharge capacity of 521 mAh g−1 at the 104th discharge.