Two novel 2D energetic metal–organic frameworks (MOFs), namely, [Pb(BTF)(H₂O)₂]_n (1) and [Ba(BTF)(H₂O)₄]_n (2), that possess the combined advantages of tetrazole and furazan rings were successfully synthesized. Their crystal structures were determined by single-crystal X-ray diffraction and fully characterized by elemental analysis and FT-IR spectroscopy. Their thermal stability and sensitivity were also investigated. The MOFs have good thermal stability (T_dec > 250 °C) and are insensitive to impact (IS > 25 J) and friction (FS > 360 N), and also have good oxygen balance (Ω > −20%). Crystal structure analyses reveal that the two compounds have densities up to 3.382 g cm⁻³ and 2.336 g cm⁻³, respectively, and excellent physicochemical properties. Tetrazole and furazan rings as ligands can commendably increase the densities and oxygen balance of energetic MOFs, thereby enhancing their detonation performance. We anticipate that this work will open a new direction for the development of energetic MOFs. Moreover, (1) exhibits outstanding catalytic performance for ammonium perchlorate (AP). When the supramolecular complex was added in 10 wt% amount, the high-temperature decomposition peak of AP advanced by 95 °C and the reaction rates enhanced by lowering the activation energy.