Room temperature sodium-sulfur (RT-Na/S) batteries have recently regained a great deal of attention due to their high theoretical energy density and low cost, which make them promising candidates for application in large-scale energy storage, especially in stationary energy storage, such as with electrical grids. Research on this system is currently in its infancy, and it is encountering severe challenges in terms of low electroactivity, limited cycle life, and serious self-charging. Moreover, the reaction mechanism of S with Na ions varies with the electrolyte that is applied, and is very complicated and hard to detect due to the multi-step reactions and the formation of various polysulfides. Therefore, understanding the chemistry and optimizing the nanostructure of electrodes for RT-Na/S batteries are critical for their advancement and practical application in the future. In the present review, the electrochemical reactions between Na and S are reviewed, as well as recent progress on the crucial cathode materials. Furthermore, attention also is paid to electrolytes, separators, and cell configuration. Additionally, current challenges and future perspectives for the RT-Na/S batteries are discussed, and potential research directions toward improving RT-Na/S cells are proposed at the end.