The tautomerism of all possible forms of 5‐aminotetrazole (AT1–AT7) in the gas phase and continuum solvent was studied theoretically. The calculations were separately performed at the MP2 and CAM‐B3LYP levels of theory, using the 6‐311++G(d,p) basis set. It was found that 5‐aminotetrazole in the 2H form (AT1) is the most stable isomer in both the gas phase and in solution. In addition, the aggregation of various isomers of 5‐aminotetrazole with hydrazine was investigated in the gas phase and in solution. Finally, the standard enthalpy of formations of the different structures of hydrazinium 5‐aminotetrazolate was determined in the gas phase. Using the calculated standard enthalpy of formation of different structures of hydrazinium 5‐aminotetrazolate in the gas phase and considering their Boltzmann population ratios, a single value has been reported for the standard enthalpy of formation of hydrazinium 5‐aminotetrazolate considering all of the tautomers. The calculated values are in excellent agreement with the experimentally reported heat of formation for the hydrazinium 5‐aminotetrazolate.