This paper provides the first in-depth study of energetic methoxy-NNO-azoxy compounds. 3-Amino-4-(methoxy-NNO-azoxy)furazan (7) is a useful precursor to a number of high-enthalpy substituted (methoxy-NNO-azoxy)furazans enriched with explosophoric functionalities (azofurazan 8, nitrofurazan 9, azoxyfurazan 10 and methylene dinitramine 11). It was shown for the first time that the interaction of nitroso compounds with salts of O-substituted N-nitrohydroxylamines leads to the formation of corresponding azoxy-oxy [N(O)=N–O] compounds, as exemplified by the reaction of 3-amino-4-nitrosofurazan (15) with the ammonium salt of O-methyl-N-nitrohydroxylamine (16) to give 3-amino-4-(methoxy-NNO-azoxy)furazan (7). This novel approach turned out to be the most suitable for the multigram synthesis of aminofurazan 7. The resulting (methoxy-NNO-azoxy)furazans 7–11 have good thermal stability (onset decomposition temperatures 148–238 °C), high experimental enthalpies of formation (1435–2750 kJ∙kg–1) and acceptable densities (1.57–1.75 g∙cm–3). In terms of detonation performance, all synthesized compounds (detonation velocities D = 7.9–8.5 km·s–1, detonation pressures PC–J = 26–32 GPa) lie between 1,3,5-trinitro-1,3,5-triazinane (RDX) (D = 8.9 km·s–1, PC–J = 36 GPa) and N-methyl-N-(2,4,6-trinitrophenyl)nitramide (Tetryl) (D = 7.6 km·s–1, PC–J = 26 GPa). The sensitivity study was performed and the results were compared to those for prevalent energetic materials. We have shown the extent to which introduction of the methoxy-NNO-azoxy group into a molecule can be used to tune the crucial properties of energetic materials (enthalpy of formation and thermal stability).