The thermal decomposition behaviors of AP and AP/Catocene were studied by DSC and TG analysis, and the activation energy E_a1, E_a2, E_a3 and the pre-exponential factor lgA₁, lgA₂, lgA₃ were calculated by Ozawa and Kissinger method. In results of DSC, there is a additional exothermic peaks at 180 ℃ with Catocene which belongs to the decompostion of Catocene. GFP makes the values of E for low and high temperature decomposition reaction of AP decrease 13.2 kJ·mol^-1 and 7.1 kJ·mol^-1, respectively. The most probable mechanism functions of the thermal decomposition reaction of AP and AP/catocene were determined based on Satava-Sestak method. The mechanism of accelerating effects was discussed.