(Hetero)Aryl fluorosulfates (ArOSO2F/ArOFs) emerged as a versatile synthon in "click chemistry," attracting the interest of chemists owing to their extensive applications in fields such as biology, medicine, materials, and polymers. Readily prepared from widely available phenolic compounds in nature, fluorosulfates serve as a economical, efficient, and environmentally friendly alternative to trifluoromethane sulfonates. In recent years, fluorosulfates have attracted research attention as emerging electrophilic reagents in transition‐metal‐catalyzed coupling reactions. The development of a broad range of coupling reactions will considerably expand their applications in interdisciplinary fields. This review summarized the synthesis methods for fluorosulfates and their instances as coupling partners in various transition‐metal‐catalyzed reactions. [ABSTRACT FROM AUTHOR]