4-(Trifluoromethyl- or pentafluorosulfanyl)-substituted mono- and poly-1,2,3-triazole compounds were synthesized using Cu(I)-catalyzed 1,3-dipolar azide and fluorinated alkyne cycloaddition reactions. This methodology gave highly regioselective 4-substituted 1,2,3-triazole products. The SF₅-containing materials (1b–6b) exhibit higher densities and more favorable detonation properties relative to their analogs with a CF₃ substituent (1a–6a). Fluorinated triazene-(1,2,3-triazole) compounds (5a, 6a, 5b, 6b) have the most useful detonation properties based on calculations (Cheetah 5.0), and are comparable to those of TNT. These compounds are thermally stable (>270 °C) except for 1b, and are insensitive to impact. All of the new compounds were fully characterized via elemental, spectral (¹⁹F, ¹H, ¹³C NMR), and differential scanning calorimetry (DSC) analyses. Compounds 3a and 4a were also structured using single crystal X-ray diffraction.