The ever‐growing pursuit of high energy density batteries has triggered extensive efforts toward developing alkali metal (Li, Na, and K) battery (AMB) technologies owing to high theoretical capacities and low redox potentials of metallic anodes. Typically, for new battery systems, the electrolyte design is critical for realizing the battery electrochemistry of AMBs. Conventional electrolytes in alkali ion batteries are generally unsuitable for sustaining the stability owing to the hyper‐reactivity and dendritic growth of alkali metals. In this review, we begin with the fundamentals of AMB electrolytes. Recent advancements in concentrated and fluorinated electrolytes, as well as functional electrolyte additives for boosting the stability of Li metal batteries, are summarized and discussed with a special focus on structure–composition–performance relationships. We then delve into the electrolyte formulations for Na‐ and K metal batteries, including those in which Na/K do not adhere to the Li‐inherited paradigms. Finally, the challenges and the future research needs in advanced electrolytes for AMB are highlighted. This comprehensive review sheds light on the principles for the rational design of promising electrolytes and offers new inspirations for developing stable AMBs with high performance.

A spontaneous microcell corrosion mechanism of Zn anode in a static ZnSO₄ solution was revealed via localized electrochemical analysis techniques. Zn corrosion could induce its self-passivation, causing the formation of plate-like Zn₄SO₄(OH)₆·xH₂O.