Recently, sulfonylation reactions using potassium/sodium metabisulfite as the sulfur dioxide surrogate have been developed rapidly. In most cases, the transformations go through radical processes with the insertion of sulfur dioxide under mild conditions. Additionally, transition metal catalysis is applied in the reactions for the synthesis of sulfonyl-containing compounds. Among the approaches, photoinduced conversions under visible light or ultraviolet irradiation are also involved. In this updated report, the insertion of sulfur dioxide from potassium metabisulfite or sodium metabisulfite is summarized.