<p>Aromatic nitrogen-rich heterocycles, furoxan and 1,2,4-triazine, are attractive, flexible molecular backbones for high-energy materials owing to their high nitrogen and energy content. The merger of these two rings results in a fused heterocycle, (1,2,4-triazin-3-yl)furoxan, and the introduction of N-oxide groups markedly improves the oxygen balance and energy density. To understand the positional influence in azole N-oxides, we designed a series of (1,2,4-triazin-3-yl)furoxan derivatives, systematically varying the N-oxide position. All the designed (1,2,4-triazin-3-yl)furoxan derivatives show a high enthalpy of formation (&gt; 468&#xa0;kJ/mol), high density (&gt; 1.81&#xa0;g/cm³), along with superior detonation pressure (&gt; 28.69 GPa), velocity (&gt; 8.23&#xa0;km/s), and moderate sensitivity (Safety Factor &gt; 20). Most of the (1,2,4-triazin-3-yl)furoxan derivatives exhibited remarkable energetic performance, comparable to or better than that of RDX. We then used an electrostatic surface potential analysis, interaction region indicator plots, molecular planarity parameters, and multicenter bond index analysis to probe their electronic structure, intermolecular interactions, and aromatic character. The physicochemical properties of (1,2,4-triazin-3-yl)furoxan derivatives show that switching the amine for nitro functional groups and making an alteration to the N-oxide position in the oxadiazole ring have a notable impact on key energetic and safety properties.</p> Graphical abstract <p></p>