A series of fused-ring energetic materials, i.e., 3,6-dinitro-1,4-di(1H-tetrazol-5-yl)-pyrazolo [4,3-c]pyrazole (DNTPP, compound 2) and its ionic derivatives (compounds 3−8), were designed and synthesized in this study. The molecular structures of compounds 2, 3, 6, 7•2H 2 O, and 8 were confirmed using single-crystal X-ray diffraction. Their physicochemical and energetic properties, such as density, thermal stability, heat of formation, sensitivity, and detonation properties (e.g., detonation velocity and detonation pressure), were also evaluated. The results indicate that DNTPP and most of its ionic derivatives are extremely thermally stable and insensitive toward mechanical stimuli. In particular, the thermal decomposition temperature of compound 3 is up to 329 °C, while compounds 7 and 8 are very insensitive (impact sensitivity: >20 J; friction sensitivity: >360 N). Compounds 2, 3, and 6 possess good comprehensive properties, including excellent thermal stability, remarkable low sensitivities, and favorable detonation performance. These features show that DNTPP and its ionic derivatives have considerable promise as thermally stable and insensitive energetic materials.