1-((Cyano-1-methylethyl) azo) formamide (CABN) is an azo initiator that has the inherent property of being decomposed at high temperatures with considerable amounts of heat generated. The thermal hazard of CABN is the main consideration in the occurrence of serious accidents. In this study, differential scanning calorimetry (DSC) was used to obtain the heat flow profiles and thermodynamic parameters of pure and impure CABN at various heating rates. The gaseous products and decomposition residues corresponding to each mass loss stage of CABN were judged by a thermogravimetry-mass spectrometer (TG-MS) and infrared spectrometer (IR). The optimal thermal decomposition reaction path of CABN was simulated and determined by the Gaussian software. The Materials Studio software was used to simulate the front-line orbits and energy gaps of CABN and its mixture to determine the influence of impurities on the thermal stability of CABN. Above results showed that the addition of the impurities caused an increased thermal decomposition risk of CABN. N₂, CO, CO₂, CH₄N₂O, 2-aminoisobutyronitrile, and isobutyronitrile were the potential products as a result of the thermal decomposition of CABN. The results of this study are expected to provide the fundamentals for safely handling CABN in preparation, production, transportation, and storage purposes.