With the demand to develop outstanding-performance energetic materials, 1-(dinitromethyl)-4,4',5,5'-tetranitro-1H,1'H-2,2'-biimidazole (DNM-TNBI) emerged as a great contender (D: 9102 m·s-1; P: 37.6 GPa). However, the relatively poor thermal stability (Td: 142 ℃) limits its practical application. In this study, DNM-TNBI as a host molecule to synthesize two new energetic open-framework materials by effectively coordinated with different cations. Their supramolecular structures were investigated and indicated that [DNM-TNBI2-][2NH4+] and [DNM-TNBI2-][2K+] can be classified as a new energetic hydrogen-bonded ammonium framework (EHAF) and an energetic metal organic framework (EMOF). Meanwhile, their thermal stabilities are higher than that of DNM-TNBI and have satisfactory detonation performance ([DNM-TNBI2-][2NH4+], D: 8050 m·s-1, P: 26.4 GPa; [DNM-TNBI2-][2K+], D: 8301 m·s-1, P: 30.8 GPa).