Organic electrosynthesis is one of the most hectic areas of research currently, and the chemistry of electrosynthesis has a profound effect on organic synthesis and green chemistry. Sulfinate salts are versatile reagents that have been widely used as many synthetic precursors under chemical oxidizing or transition-metal catalysis conditions in organic chemistry during the past few decades. In particular, great achievements in the development of electrochemical transformations of sulfinate salts have been made recently. In this review, successes achieved until the end of 2019 on the chemistry of electrochemical transformation of sulfinate salts in organic synthesis, as well as insights into the reaction mechanism, will be intensively presented and discussed.