In this chapter, we have summarized some special and representative transformations using DMSO as a green solvent in organic synthesis over the last 5 years. In contrast to previous reviews, we focus more on the in situ activation pattern of DMSO by summarizing different fragmentation processes of DMSO to show the reaction initiation pathway. For example, Pummerer-type, Selectfluor-enabled, electrocatalytic-enabled, and photocatalytic-enable activation of DMSO were classified and discussed in detail. For each activation pattern, several recent representative transformations are listed, along with their selected products to show their generality, while a detailed mechanism is also provided after each example to facilitate the reader's understanding and to illustrate the chemical principles. We believe that this chapter provides a unique perspective to lead to a better understanding of the DMSO-mediated transformations and provides integrated information for chemical researchers who are keen to select a method for DMSO activation.