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The direct α‐Csp²H functionalization and thiomethylation of α‐oxoketene dithioacetals (DTAs) has been accomplished with dimethyl sulfoxide (DMSO) in the presence of iodine and a copper(I) salt for the first time. A prerequisite is the in situ iodination of the α‐Csp² atom of dithioacetals that could offer other reaction channels. The operationally simple one‐pot protocol includes region‐defined consecutive iodination and sulfenylation of the challenging α‐Csp²H bond of dithioacetals employing cheap and readily available reagents. DMSO here plays a dual role as thiomethyl source and solvent.