Aryl fluorosulfates are versatile building blocks in organic synthesis and have gained increasing attention in SuFEx (Sulfur Fluoride Exchange) click chemistry. They are easily and conveniently prepared from phenols using sulfuryl fluoride SO₂F₂ as a low-cost sulfonyl fluoride provider. Recently, they served as less toxic and more atom economical alternatives to triflates in an impressive number of carbon–carbon and carbon-heteroatom cross-coupling reactions. In this review, we summarize the current advances and developments in applying aryl fluorosulfates as electrophilic partners in cross-coupling reactions.