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.