The click chemistry of sulfur(VI) fluoride exchange (SuFEx) has facilitated the widespread application of sulfur-fluoride compounds such as sulfonyl fluorides, fluorosulfates, and sulfamoyl fluorides in various fields, especially in the development of F-18 ligands for PET (positron emission tomography) imaging. In recent years, the prominent progress of sulfur-[F-18]fluoride compounds has been achieved through the combination of F-18 and sulfur-fluoride chemistry. These compounds serve as potential F-18 tracers, F-18 synthons, and reagents for F-18-fluorination, thereby complementing the range of F-18 ligands, typically C-F-18 structures, used in PET studies. This review aims to provide an overview of S-F-18 labeling reactions through examples of relevant F-18 compounds and highlight the advancements and breakthroughs achieved in the past decade.