A novel ferric perfluorooctanoate Fe(PFO)(3) was synthesized through a simple method with high yield. FT-IR spectra, UV-vis spectra, ESI-MS, ICP-OES and TGA were used to characterize Fe(PFO)(3). Fe(PFO)(3) was used as catalyst to promote the thermal decomposition of ammonium perchlorate (AP). The thermal decomposition of ammonium perchlorate (AP) in the presence or absence of Fe(PFO)(3) was investigated by TGA and Differential Scanning Calorimeter (DSC). The data obtained from TGA and DSC indicates that Fe(PFO)(3) could obviously reduce the high-temperature decomposition temperature of AP and strength the total heat release of AP. Kissinger method was used to calculate activation energy of different specimens according to DSC data, and the results indicated that Fe(PFO)(3) can decrease the activation energy of AP/Fe(PFO)(3) mixture. To prove the catalytic mechanism of Fe(PFO)(3), thermal decomposition products of Fe(PFO)(3) were collected with tube furnace. XRD was used to study the phase composition of thermal decomposition products of Fe(PFO)(3). The XRD result shows that the catalysis of Fe(PFO)(3) may be from the FeF2,FeF3 and Fe2O3 of its thermal decomposition. (C) 2016 Elsevier B.V. All rights reserved.