Sodium sulfinates have been widely utilized as sulfonyl radical precursors for preparing a diverse array of value-added sulfur-containing compounds (sulfones, sulfonamides, sulfonates, thiosulfonates, etc.) through S-C, S-N, S-O and S-S bonds formation reactions. Organic electrosynthesis has become an attractive alternative to conventional methods for redox reactions because it utilizes electric current instead of chemical redox agents. As such, the electrochemical generation of sulfonyl radicals from sodium sulfinates and their applications in organic electrosynthesis have attracted much attention. In this review, the recent advances in the electrochemical sulfonylation of organic compounds involving sodium sulfinates as sulfonyl radical precursors since 2015 were reviewed, along with related reaction mechanisms.