Heterocycles are a highly valuable class of complex scaffolds that are involved in a various kind of well-known organic compounds of industrial and pharmacological importance.Sultine,an important class of sulfur-containing heterocy-clic compounds,plays central roles in medicine,biology and material science.The sulfur atom in sultine is located at a vertex of a stable pyramid without identical substituents,making it a chiral center with potential applications in asymmetric synthe-sis.The asymmetry of sultine can be easily eliminated by oxidizing it into sultone.In addition,sultines have shown to be versatile intermediates in organic synthesis.They can act as useful synthons with hidden bifunctionality:opening the hetero-cycle at the S-O bond leads to the simultaneous appearance of two functional groups in the product.Despite their potential,the chemical research of sultines have been long neglected and underdeveloped due to their inaccessibility.Only recently,some research groups have discovered protocols for the preparation of these heterocycles and explored their properties using methods such as visible light-induced radical homolytic substitution cyclization and radical polar crossover cyclization,and so on.It is worth noting that although sultines have been discussed in a few reviews,they are not systematic but very frag-mentary.Owing to the increasing interest in studies on sultines and their transformations.The synthesis methods,physical properties and applications of sultines are systematically summarized in the past 130 years.The synthetic tactics are reviewed by highlighting their product diversity,selectivity and applicability,along with the mechanistic rationale where possible.Ad-ditionally,the chemical transformations of sultines,including photolysis,thermolysis,ring-opening reactions,oxida-tion/reduction reactions,and rearrangement reactions,are demonstrated.The usefulness of sultines in synthesis,medicine and materials is described as well.Finally,the development status of sultine compounds is reviewed,and a future perspective is provided,in order to offer reference for researchers engaged in sultine chemistry.