<p>Inspired by high nitrogen and oxygen content and a unique internal onium salt structure, twenty-seven zwitterionic molecules containing an oxatriazole explosophore were designed and further explored. Their electronic structures, heats of formation (HOF), detonation properties, thermal stabilities, thermodynamic properties, and electrostatic potential were systematically investigated by density functional theory. The calculation results indicate that after ionization of the oxatriazole ring, the bond length shows an average trend, providing impetus for the formation of energetic oxatriazole cationic salts. And energetic materials with diazo substituted structures are more extensive, which is consistent with the results of electronic structure. Interaction region indicator studies have shown that the more places and wider the range of van der Waals forces exist in similar energetic inner salts, the higher the calculated density of the substance. It has been proved that the atomization method is superior for calculating heat of formation of energetic inner salts. When the carbon atom of the triazole ring is replaced with a nitrogen atom, detonation velocity increases by 8–12%, and detonation pressure increases by 20–28%. This work could provide interesting inspiration for the hunting of novel zwitterionic energetic materials.</p>