Thermolysis of dimethylanilinium nitrates (DMAN) has been carried out by TG, DTA, ignition delay, impact and friction sensitivity measurements. Although kinetics of the thermal decomposition of these salts were evaluated by fitting TG data in nine-mechanism-based kinetic models, only Avrami-Erofeev (n = 2, 3) and contracting area (n = 2) gave the best fits. A reaction scheme accounting for the decomposition products is proposed; it involves proton transfer leading to the formation of an arylamine and HNO3. The other probable routes (evolution of NH,) have also been suggested. The aryl nucleus seems to be oxidized by NO2, HNO3 or its decomposition products prior to ignition, and gaseous products are formed.