A simple method, which takes place quickly in 5 min, is developed for the N-triflination of pyrazolones using CF3SO2Na (Langlois reagent) and phenyliodine(iii)bis(trifluoroacetate) (PIFA). This reaction takes place at the imine nitrogen centre instead of the more reactive C4-position, forming a new N-S bond. A variety of pyrazolone derivatives were subjected to the reaction. Unlike the previous reports on sulfenylation or sulfonylation of pyrazolone, wherein the corresponding C-S bond is formed, this new method leads to the formation of the hetero-hetero atom bond (N-S bond) at room temperature.