Heat-resistant explosives play an irreplaceable role in specialized applications. Two energetic metal-organic frameworks (EMOFs), potassium 4,4'-oxybis[3,3'-(5-tetrazol)]furazan and potassium (1,2,4-triazol-3-yl)tetrazole, featuring a three-dimensional metal-organic framework structure, were first synthesized and characterized by chemical (1H NMR, 13C NMR, MS, IR spectroscopy, and single-crystal XRD) and physicochemical analyses (sensitivity toward friction, impact, electrostatic, and DSC-TGA test). The new 3D EMOFs were found to show high thermostability, highly positive heat of formation, and suitable sensitivities. The Hirshfeld surface was further analyzed in order to explore the effect on sensitivities. Their detonation properties (detonation velocity, detonation pressure, etc.) were calculated by the EXPLO5 program. K2NTT exhibits extremely high decomposition temperatures of up to 361 °C; meanwhile, its detonation performance is comparable to that of TATB and other energetic potassium salts, which makes it a promising heat-resistant explosive.