Dimethyl sulfoxide (DMSO) is one of the most commonly applied organic solvents in chemical transformations and is utilized widely in industrial processes as well. During the past decades, numerous procedures using DMSO as a reaction reagent have been developed and published. In this review, the main developments on the employment of DMSO as sources of £Me, £SMe, £SO2Me, as an oxidant etc. have been summarized and discussed. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.