In the past decades, DMSO has been widely used not only as a common solvent but also as an environmentally benign oxidant in various organic transformations. Most strikingly, DMSO can be used as a sulfur source to construct methylthiolated building blocks of potential biologically active molecules, which is a remarkable achievement in the field of organic sulfur chemistry. The purpose of this review article is to summarize and discuss the main developments in the application of DMSO as a methylthiolating reagent to introduce the -SMe functionality in organic synthesis.