Pummerer rearrangement reactions generate sulfur (II) oxidation state from sulfur (IV) starting materials in the presence of activating reagents. We found unprecedented transformation of vinyl sulfoxide; disulfide formation reactions mediated by atmospheric pressure of carbon dioxide in extended Pummerer rearrangement reactions. Only under CO₂ atmosphere, we observed moderate to high yields of disulfide starting from sulfur (IV) starting materials. Investigations on the reaction mechanism revealed that the degradation of the starting materials and the products was significant in the absence of CO₂. Further evidence for the suggested reaction mechanism was obtained by a cross-over experiment and a radical trapping reagent.