In recent years, molecular perovskite energetic materials have attracted more attention because of their simple synthesis processes, high thermal stabilities, excellent performances, and great significance as a design platform for energetic materials. To explore the possibility of the application of molecular perovskite energetic materials in heat-resistant explosives, four silver(I)-based molecular perovskite energetic compounds, (H2A)[Ag(ClO4)3], where H2A = piperazine-1,4-diium (H2pz2+) for PAP-5, 1-methyl-piperazine-1,4-diium (H2mpz2+) for PAP-M5, homopiperazine-1,4-diium (H2hpz2+) for PAP-H5, and 1,4-diazabicyclo[2.2.2]octane-1,4-diium (H2dabco2+) for DAP-5, were synthesized by a one-pot self-assembly strategy and structurally characterized. The single-crystal structures indicated that PAP-5, PAP-M5, and DAP-5 possess cubic perovskite structures while PAP-H5 possesses a hexagonal perovskite structure. Differential thermal analyses showed that their onset decomposition temperatures are >308.3 °C. For PAP-5 and DAP-5, they have not only exceptional calculated detonation parameters (D values of 8.961 and 8.534 km s-1 and P values of 42.4 and 37.9 GPa, respectively) but also the proper mechanical sensitivity (impact sensitivities of ≤10 J for PAP-5 and 3 J for DAP-5 and friction sensitivities of ≤5N for both PAP-5 and DAP-5) and thus are of interest as potential heat-resistant primary explosive components.