A novel Ag(I) energetic MOF [Ag16(BTFOF)9]n·[2(NH4)]n () assembled with Ag(iI ions and a furazan derivative, 4,4'-oxybis[3,3'-(1H-5-tetrazol)]furazan (H2BTFOF) was successfully synthesized and structurally characterized, featuring a three-dimensional porous structure incorporating ammonium cations. The thermal stability and energetic properties were determined, revealing that the 3D energetic MOF had an outstanding insensitivity (IS > 40 J), an ultrahigh detonation pressure (P) of 65.29 GPa and a detonation velocity (D) of 11.81 km cm(-3). In addition, the self-accelerating decomposition temperature (TSADT) and the critical temperature of thermal explosion (Tb) are also discussed in detail. The finding exemplifies that the assembly strategy plays a decisive role in the density and energetic properties of MOF-based energetic materials.