AbstractThe synthesis of three new families of heterocyclic‐based salts was undertaken and accomplished. Three triazole systems, 1H‐1,2,4‐triazole, 4‐amino‐1,2,4‐triazole, and 1H‐1,2,3‐triazole, were used as proton bases with nitric (HNO3), perchloric (HClO4), and dinitramidic (HN(NO2)2) acid systems. In all cases, stable salts were recovered and fully characterized by vibrational spectra (IR, Raman), multinuclear NMR spectroscopy, material balance, density measurements, and elemental analyses, as well as DSC, TGA and initial safety testing (impact). Many of these salts have melting points well below 100 °C, yet high decomposition onsets, defining them as new, highly energetic members of the well known class of materials identified as ionic liquids. Additionally, the single crystal X‐ray diffraction study of 1,2,4‐triazolium perchlorate was investigated, revealing the expected structure.