In addition to the three classical methods for adjusting the performance of energetic complexes, in order to explore the influence of different bonding types on the performance of energetic materials, we designed ionic salts PZCA•HClO 4 (3) and ECPs [Ag(PZCA)ClO 4 ] n (4) with PZCA(1H-pyrazole-4carbohydrazide) as the ligand. They use the same ligands and oxidizing acids and also have the same N/O number. On the basis of their structures and compositions confirmed by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction, the characterization of physical and chemical properties shows that 4 has better thermal decomposition behavior (ΔT = 30 °C), more suitable mechanical sensitivity (IS = 5 J, FS = 9 N), and more outstanding initiation performance. After studying the decomposition mechanism, we find that different types of bonds (H bond or coordination covalent bond) lead to different decomposition mechanisms (redox reaction or free radical reaction) and, finally, show great differences in explosive properties.