Sulfur and fluorine occupy crucial positions in main group chemistry because these two elements form a variety of compounds with versatile bond modalities and unique functionalities. Among sulfur-fluorine compounds, the importance of SF4 and its derivatives is recognized in the literature. The amphoteric nature of SF4 results in its rich Lewis acidic and basic reactivities; the reactions with F- acceptors and donors yield [SF3]+ and [SF5]- salts, respectively. Lewis basic molecules can also form adducts with SF4via various interaction motifs. The deoxofluorinating properties of SF4 have been used by organic chemists to selectively introduce fluorine atoms in specific substrates, extending also to industrial applications. Although the properties and reactivity of SF4 have been studied since its first synthesis, the recent progress in the SF4-related chemistry is striking, involving various fields of chemistry. In this Frontier article, recent advances, mainly the last ten years, in syntheses and structures of SF4-related compounds including its cationic and anionic derivatives and adducts with Lewis bases are concisely reviewed. Their uses in fundamental and applied inorganic chemistries are also described.