Designing and synthesizing more advanced high-energetic materials for practical use via a simple synthetic route are two of the most important issues for the development of energetic materials. Through an elaborate design and rationally selected molecular components, two new metal-free hexagonal perovskite compounds, which are named as DAP-6 and DAP-7 with a general formula of (H2dabco)B(ClO4)3 (H2dabco2+ = 1,4-diazabicyclo[2.2.2]octane-1,4-diium), were fabricated via an easily scaled-up synthetic route using NH3OH+ and NH2NH3+ as B-site cations, respectively. Compared with their NH4+ analog ((H2dabco)(NH4)(ClO4)3; DAP-4), which has a cubic perovskite structure, DAP-6 and DAP-7 have higher crystal densities and enthalpies of formation, thus exhibiting higher calculated detonation performances. Specifically, DAP-7 has an ultrahigh thermal stability (decomposition temperatures (Td) = 375.3 °C), a high detonation velocity (D = 8.883 km·s‒1), and a high detonation pressure (P = 35.8 GPa); therefore, it exhibits potential as a heat-resistant explosive. Similarly, DAP-6 has a high thermal stability (Td = 245.9 °C) and excellent detonation performance (D = 9.123 km·s‒1; P = 38.1 GPa). Nevertheless, it also possesses a remarkably high detonation heat (Q = 6.35 kJ·g‒1) and specific impulse (Isp = 265.3 s), which is superior to that of hexanitrohexaazaisowurtzitane (CL-20; Q = 6.23 kJ·g‒1; Isp = 264.8 s). Thus, DAP-6 can serve as a promising high-performance energetic material for practical use.