To further balance the energy and safety of 5-nitro-3-(trinitromethyl)-1H-1,2,4-triazole, four nitrogen-rich energetic ionic salts were synthesized using 2-(5-amino-1H-1,2,4-triazole-3-yl) acetic acid as a starting material through a silver salt substitution reaction. The structures of all new compounds were characterized using nuclear magnetic resonance, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and single crystal X-ray diffraction. The results indicate that the ammonium salt, hydrazine salt, and guanidine salt of 5-nitro-3-(trinitromethyl)-1H-1,2,4-triazole exhibit higher initial decomposition temperature than that of the precursor. Moreover, the hydrazine salt and guanidine salt belong to the different crystal systems with distinct crystal packing arrangements and densities. However, they share consistent characteristics in terms of intermolecular weak interactions, with the H…O interaction being the predominant contributor. With the decreasing of the ratios of N…O and O…O interactions, the sensitivity of the nitrogen-rich energetic ionic salts to mechanical stimuli decreases. Finally, the analysis of the distribution of molecular electrostatic potential supplements the explanation for the change in impact sensitivity of 5-nitro-3-(trinitromethyl)-1H-1,2,4-triazole after salt formation. Among the four ionic compounds, the hydrazine salt exhibits outstanding detonation performance (D=8634 m·s-1, p=30.2 GPa, Isp=263.5 s) with relative high sensitivity. In contrast, the triaminoguanidine salt demonstrates excellent overall performance. It has a detonation velocity comparable to that of the hydrazine salt (D=8627 m·s-1), a heat of formation nearly 1.4 times greater than that of the precursor (ΔHf=0.644 kJ·g-1), and a low mechanical sensitivity (IS=10.3 J, FS=150 N).