Langlois’ reagent (trifluoromethanesulfinate salt) has been proven to be a valuable reagent for the synthesis of various classes of molecules, mainly trifluoromethylated compounds, in academic, biological and industrial research. Synthetic uses of Langlois’ reagent in organic transformations of aromatic and heteroaromatic compounds, alkenes, alkynes, boronic acids, carboxylic acids, and etc are discussed.This review aims to demonstrate the ongoing utility of Langlois’ reagent in the preparation of various classes of organic compounds. Furthermore, to address the recent collective papers, the current review summarizes and comprehensively describes manuscripts on synthetic applications of Langlois’ reagent since 2015 until today.