A series of energetic nitrogen-rich salts comprised of a 5-(trinitromethyl)tetrazolate anion and high-nitrogen cations was synthesized by simple and efficient chemical routes from readily available commercial reagents. These energetic materials were fully characterized by IR and multinuclear NMR (1H, 13C, 14N) spectroscopy, elemental analysis, and differential scanning calorimetry (DSC). Additionally, the structure of an energetic salt containing the 3,6,7-triamino-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazolium cation was confirmed by single-crystal X-ray diffraction. The synthesized compounds exhibit decent experimental densities (1.648–1.845 g cm−3) and positive enthalpies of formation (up to 725.5 kJ mol−1) and, as a result, superior detonation performance (detonation velocities 8.2–9.2 km s−1 and detonation pressures 28.5–37.8 GPa), which is comparable to or even exceeding those of commonly used booster explosive PETN. On the other hand, high mechanical sensitivity of several novel 5-(trinitromethyl)tetrazolate salts along with their high combined nitrogen-oxygen content (>81%) and excellent detonation performance render them environmentally friendly alternatives to lead-based primary explosives.