In this work, a fused-ring [1,2,5]oxadiazolo[3,4-b]pyridine 1-oxide framework with multiple modifiable sites was utilized to develop novel energetic materials with multiple hydrogen bonds. The prepared materials were characterized, and their energetic properties were extensively investigated. Among those studied, compound 3 exhibited high densities of 1.925 g cm-3 at 295 K and 1.964 g cm-3 at 170 K, with high detonation performances (Dv: 8793 m s-1 and P: 32.8 GPa), low sensitivities (IS: 20 J, FS: 288 N), and good thermal stability (Td: 223 °C). N-Oxide compound 4 had higher-energy explosive (Dv: 8854 m s-1 and P: 34.4 GPa) and low sensitivities (IS: 15 J and FS: 240 N). Compound 7 with a high enthalpy group (tetrazole) was determined as a high-energy explosive (Dv: 8851 m s-1, P: 32.4 GPa). Notably, the detonation properties of compounds 3, 4, and 7 were similar to high-energy explosive RDX (Dv: 8801 m s-1 and P: 33.6 GPa). The results indicated that compounds 3 and 4 were potential low-sensitivity high-energy materials.