AbstractAmmonium dinitramide (ADN), NH4N(NO2)2 is being considered as one of the potential new energetic oxidizers for composite propellants. In this study, ADN crystals, prills and two ADN‐based propellants having different relative amounts of ingredients were characterized. The concentration of the crystals and the prills samples was determined using ion chromatography. The thermal behavior of the crystals, prills and propellants was studied using DSC, simultaneous TG‐DTA‐FTIR‐MS, ARC (accelerating rate calorimeter), HFC (heat flux calorimeter) and INC (isothermal nanocalorimeter). Decomposition of ADN was observed from all of the samples at temperatures above the melting point of ADN (~ 92 °C). Formation of N2O, NO2, H2O, CO2, CO, N2 and NO was detected during the ADN decomposition. The thermal stability of the ADN samples at temperatures below the melting point of ADN was studied. Early solid decomposition of ADN, which generates N2O and H2O, was observed at 60 °C. Electrostatic discharge (ESD) and impact sensitivity of the ADN samples were determined. The crystals and prills are sensitive to impact, while the two propellants are relatively less ESD and impact sensitive.