During thermal decomposition of azobisisobutyronitrile (AIBN), the endothermic process of phase transition disturbed exothermic decomposition, which brought deformation in its thermal graphs. Therefore, exact kinetic parameters of the decomposition could not be obtained by the existing kinetics analytic models, and the accurate enthalpy data of the decomposition and phase transition were not available. Two methods, i.e., a solvent method and a mathematical method, were introduced in this paper to resolve the coupling phenomenon. In the former method, AIBN was dissolved into aniline to eliminate the endothermic process and obtain curves of the liquid-state decomposition. In the latter method, MATLAB software was employed to get the "pure" exothermic decomposition curve without the influence of phase transition by fitting coupling curves within the section after the transition point and extrapolating to the initial stage of decomposition. Moreover, the kinetic parameters of the "pure" exothermic decomposition of AIBN obtained by the mathematical fitting agreed with the results from the solvent method, verifying the accuracy of the decoupling. The research is of great significance for comprehending the exact characteristics of thermal behaviors and safety parameters of AIBN. It also provides a great help to determine the safe operating temperature and alarm temperature for processes in industry. (C) 2014 Published by Elsevier B.V.