Ammonium perchlorate (AP) is one of the most well‐known oxidizers of solid propellant. In this article, an intrinsic conductive polymer (ICP) is introduced as a green catalyst for thermal decomposition of AP. Activation energy of samples was defined by Kissinger method. A MATLAB code and Complementary method were used to derive the best model of samples decomposition reaction. It was revealed that application of nano‐porous polyaniline (NP‐PANi) changed the model of decomposition reaction of AP from(-ln1-α)14
to ()1-α-12
; as a drastic raise was observed in the maximum reaction rate, in the range of 264‐430%, at different heating rates. reaction rate constant and pre‐exponential factor were also defined. Characteristic temperatures (TSADT and Tb) have been also determined in order to evaluate the thermal stability of process. Thermodynamic parameters have been also calculated, as the results confirmed the proper catalytic activity of NP‐PANI in AP decomposition process. The obtained results would be helpful for further application of ICPs as a noble family of green catalysts used for decomposition of energetic material.