The study on the thermal behavior of some new diazoaminoderivatives was aimed to follow the structure-thermal stability-degradation mechanism correlation by means of the TG-FTIR technique and formation enthalpies. The TG-DTG-DTA curves reveal the thermal degradation in air (30–900 °C) to show two ranges as a function of temperature (time), where the gaseous species resulting by degradation are eliminated: the first, an endothermic one which is identical to that under nitrogen atmosphere and the second, an exothermal one. As made evident by the identification of the individual gaseous species by their characteristic absorbances as well as those obtained by TG-FTIR the compounds C2H2, H2C = NH, SO2, NH3, CO2, H2O, HCl are eliminated in the first domain while CO2, SO2, H2O in the second, which afforded the advancement of the most probable degradation mechanism.