The layer-by-layer assembly of molecules is ubiquitous in nature. Highly ordered structures formed in this manner often exhibit fascinating material properties. A layer hydrogen bonding pairing approach allows the development of tunable energetic materials with targeted properties. A series of unusual energetic compounds based on 1H,1'H-5,5'-bistetrazole-1,1'-diolate (1), such as the salts of 3-amino-1,2,4-triazolium (2), aminoguanidinium (3), and hydrazinium (4), and the cocrystals of 4-amino-1H-pyrazole (5), 2-methylimidazole (6), and imidazole (7), were synthesized using this strategy. The structures of the obtained products 2-7 were fully characterized by elemental analysis, IR spectroscopy, 1H NMR and 13C NMR spectroscopy, and single-crystal X-ray analysis. Their thermal decomposition behavior was studied by differential scanning calorimetry and thermogravimetry. Their mechanical sensitivities and detonation performances were also analyzed in detail. Results show that products 2-7 exhibit higher density, better detonation performances, and more excellent sensitivities than those of the same species of cation salts previously reported.