AbstractAs the “star of hope” for the next‐generation high‐energy‐density batteries, lithium–sulfur batteries (Li–S batteries) face severe challenges such as reserves, costs, and safety, which seriously restrict their practical application. Alternatively, research on multivalent metals (e.g., Mg, Ca, Al, Zn, etc.) as anodes, characterized by less reactivity and higher natural abundance, is gaining increasing attention and urgent demand. However, metal–sulfur (M–S) battery technology based on multivalent metal anodes is still in its infancy and not yet mature for practical application. This review provides insights into the challenges and prospects of multivalent M–S batteries, covering fundamental mechanisms, key issues, response strategies, and the latest advancements in flexible/micro energy storage devices. Furthermore, a general perspective and future research directions are also presented in this review. This review aims to explore opportunities for emerging multivalent M–S batteries and support the development of next‐generation high‐energy‐density energy storage systems.