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Background: I2/DMSO oxidative system catalyzed reactions have received considerable attention because they represent the advantages of being greener, efficient, atom-economical, low-cost, with mild conditions and ecofriendliness that meet with the requirements of sustainable chemistry. In recent times, the I2/DMSO oxidative system has been successfully applied in different types of organic reactions. Objective: The aim of this review is to highlight the synergistic effect of the combined use of iodine and DMSO in organic synthesis. Conclusion: It is clear from the review of the topic that a vast amount of work has been done in this area, employing an I2/DMSO system for diverse types of oxidative transformations as well as C-C and C-X bond formation reactions. In these reactions, iodine acts as a mild Lewis acid catalyst and DMSO servers as an oxidant, solvent and oxygen source. The role of iodine, DMSO as well as key intermediates involved in these reactions is discussed.