Abstract The incorporation of a trifluoromethyl (CF 3 ) group into organic compounds is of great importance in pharmaceutical, agricultural, and materials science. Trifluoromethylation based on radical intermediates, as a valuable alternative transformation using the inexpensive and stable solid sodium trifluoromethanesulfinate (CF 3 SO 2 Na; Langlois’ reagent), has attracted much attention and has become a hot research field. This review examines recent advances in radical trifluoromethylation reactions with CF 3 SO 2 Na as CF 3 source. magnified image