Abstract: | We report an efficient and scalable synthesis of azidotrifluoromethane (CF3N3) and longer perfluorocarbon‐chain analogues (RFN3; RF=C2F5, n C3F7, n C8F17), which enables the direct insertion of CF3 and perfluoroalkyl groups into triazole ring systems. The azidoperfluoroalkanes show good reactivity with terminal alkynes in copper(I)‐catalyzed azide–alkyne cycloaddition (CuAAC), giving access to rare and stable N ‐perfluoroalkyl triazoles. Azidoperfluoroalkanes are thermally stable and the efficiency of their preparation should be attractive for discovery programs. |