Sodium trifluoromethanesulfinate, CF 3 SO 2 Na, and trifluoromethanesulfonyl chloride, CF 3 SO 2 Cl, are two popular reagents that are widely used for the direct trifluoromethylation of a large range of substrates. Further, these two reagents are employed for the direct trifluoromethylsulfenylation and trifluoromethylsulfinylation, the introduction of the SCF 3 and the S(O)CF 3 group, respectively. In addition to the aforementioned reactions, the versatility of these two reagents is presented in other reactions such as sulfonylation and chlorination. This first part is dedicated to sodium trifluoromethanesulfinate.