AbstractThis paper introduces five novel high‐nitrogen content (N>50%) tetrazole derivatives with desirable physicothermal properties, high detonation and combustion performance as well as suitable sensitivities with respect to external stimuli electric spark and heat. Suitable density functional theory (DFT) and empirical methods were used to predict their crystal density, melting point, condensed phase heat of formation, enthalpy of fusion, Gibbs free energy of formation, velocity of detonation, detonation pressure, Gurney velocity, heat of detonation, power (strength), brisance, impact sensitivity, electric spark sensitivity, heat sensitivity and specific impulse. Two compounds 5,5′‐[(1Z,5Z)‐3,4‐dinitrohexaaza‐1,5‐diene‐1,6‐diyl]bis(1‐nitro‐1H‐tetrazole) and 3,3′,7,7′‐tetranitro‐3,3a,3′,3′a‐tetrahydro‐7H,7′H‐6,6′‐bitetrazolo[1,5‐e]pentazine as compared to the other new derivatives can be introduced as high performance explosives for confined explosion and oxidizers in solid propellants.