In summary, we reported the discovery of two efficient and complementary protocols for the synthesis of an unprecedented N-((trifluoromethyl)thio),N-(trifluoromethyl) amines. While one uses a shelf-stable electrophilic trifluoromethylthiolation reagent, the other employs a twochamber reactor for the in situ generation of an electrophilic trilfuoromethylthiolating reagent. The desired products have been obtained in moderate to excellent yields. The scalability of the reaction was demonstrated through the preparation of more than 3.7 grams of the desired compounds. Importantly, N(SCF3)CF3 shows high aqueous stability. We assume that this discovery will pave the way to future developments in this exciting field of research.