As an emerging high-energy substance, perovskite energetic materials remain underexplored, necessitating accelerated development in both variety and quantity. This study employed a solution-based synthesis method to produce the first perchlorate-based double perovskite energetic material, {(C6H14N2)2[Na(NH4)(ClO4)6]}n (DPE-1), along with a single perovskite energetic material, [(C4H12N2)K(ClO4)3]n (PAP-2). The chemical structures, thermal stability, detonation performance, and mechanical sensitivity of both DPE-1 and PAP-2 were systematically investigated. Single-crystal X-ray diffraction analysis revealed that DPE-1 crystallizes in a double perovskite structure within the Pa-3 space group, while PAP-2 adopts a single perovskite structure in the Pnma space group. DPE-1 exhibits significant improvements in its thermal decomposition temperature (Tdec=368.9 °C), detonation velocity (D=8858 m·s?1), detonation pressure (P=38.4 GPa), impact sensitivity (IS>40 J), and friction sensitivity (FS=20 N) compared to the previously reported periodate-based double perovskite energetic material DPPE-1. These results validate the feasibility of exploring high-performance, green primary explosives within the double perovskite structural framework. PAP-2 demonstrates comparable thermal stability (Tdec>280 °C) and detonation energy (D>8500 m·s?1, P>30 GPa) to other single perovskite energetic materials in the same series. However, it exhibits significantly higher impact sensitivity alongside markedly lower friction sensitivity.