Organofluorine chemistry is by far one of the most active fields of research in modern organic chemistry. The unique properties induced by the fluorine atom or fluorinated motifs including high lipophilicity, increased solubility and metabolic stability have witnessed the efforts for extensive development during the last years. Nowadays, fluorinated molecules are extensively used in agrochemicals as well as for pharmaceuticals 3 applications. In this span of time, several efficient procedures for the incorporation of trifluoromethyl and trifluoromethyl chalcogens have been reported in the literature through reagent and/or catalyst design as well as methodology developments. Nitrogen is also a predominant atom in life science technologies, therefore the association of amine with fluorine-based motifs such as trifluoromethyl groups has been the quest of several research groups. For example, Ntrifluoromethyl azoles has demonstrated excellent in vitro aqueous stability which might improve metabolic stability and membrane permeability compared to their N-methyl counterparts. In this context, several direct methodologies have been developed to access N-CF3 amines making use of electrophilic trifluoromethylation reagents, namely Umemoto and Togni 8 reagents or radical trifluoromethyl sources (Scheme 1A). However, these strategies offer limited scope especially with regard to the amine starting material. A breakthrough has been disclosed by the Schoenebeck group in 2017. In their study, the authors demonstrated that a wide range of trifluoromethylamines could be accessed via in situ generation of thiocarbamoyl fluoride using bench stable (Me4N)SCF3 (Scheme 1A). 11 Afterwards, several groups designed new strategies to access the key thiocarbamoyl fluoride intermediate. Finally, the group of Xu recently reported an elegant oxidative approach for the synthesis of trifluoromethyl amine reagents. The later has been used for the transfer of the N-CF3 moiety. Another way to access trifluoromethylamines relies on the use of isothiocyanates. Indeed, in 1965, Shepard initially reported that nucleophilic amines could be formed from isothiocyanates using mercury fluoride. Inspired by this precedent, the group of Schoenebeck 18 elegantly demonstrated that silver fluoride could efficiently replace the mercury-based reagent offering a practical and general way to synthesize N-trifluoromethyl carbamoyl fluoride (Scheme 1B). This procedure has been also adapted by the groups of Toste and Wilson for the synthesis of N-trifluoromethyl amides (Scheme 1B). N,N-bis(trifluoromethyl) amines represent another valuable motif due to their enhanced lipophilicity and stability in comparison to aliphatic and aromatic Ntrifluoromethylamines. Despite these interesting properties, access to N-(CF3)2 amines remain very scarce with most promising synthesis employing a combination of N,Nbis(trifluoromethyl)trifluoromethanesulphonamide with metal-based reagent (Scheme 1C). Therefore, there is a clear need for developing new motifs that could be easily and robustly accessible while modulating the properties around the nitrogen atom such as the lipophilicity (Scheme 1D). In this context, we report herein an unprecedented, mild and efficient protocol for accessing novel N-((trifluoromethyl)thio)-N-(trifluoromethylamines) starting with isothiocyanates and electrophilic trifluoromethylthiolation reagents (Scheme 1E). From a reaction design standpoint, inspired by the work of Schoenebeck, we envisioned that a trifluoromethylamino nucleophile intermediate could be first in situ generated by the reaction of isothiocyanate with silver fluoride before subsequently reacting with an electrophilic trifluoromethylthiolating source to furnish the desired compounds Table . Optimization of the reaction.