Energetic metal organic frameworks (EMOFs) are increasingly developed and have proven to be candidates for novel high energy density materials (HEDM). Here, two energetic metal complexes based on 3,5-diaminopyrazolone-4-oxime (DAPO) ligands were synthesized by simple steps and fully characterized by NMR and IR spectroscopy, X-ray single-crystal diffraction, and DSC-TG. The detonation performance was calculated using the Kamlet–Jacobs formula. The crystal densities of these complexes (C₆H₁₄N₁₂O₁₀Co (2) and C₆H₁₄N₁₂O₁₀Cd (3) are as high as 1.945 g cm⁻³ at 163 K and 2.072 g cm⁻³ at 298 K, respectively. Thermal analysis by the DSC-TG test shows that they all have good thermal stability with the highest decomposition temperatures of 287 °C and 344 °C, respectively. These two as-synthesized complexes exhibit excellent detonation performance; 2 (D = 8682 m s⁻¹, P = 34.98 GPa) and 3 (D = 8383 m s⁻¹, P = 33.78 GPa) have good detonation velocity and detonation pressure that are superior to those of TNT, which is widely used today. Thus, they show great promise for potential applications as thermally stable energetic materials.