Structures of ferrocene containing hyperbranched polyester (HBPE-Fc) was characterized by FTIR and H1 NMR. The spectroscopic analysis provided evidence of the successful modification of ferrocene toHBPE. The catalytic performances for thermal decomposition of ammonium perchlorate (AP) were investigated by DSC techniques. The kinetic parameters were computed by the Kissinger method. The results indicated that the presence of HBPE-Fc reduces the maximum decomposition reaction temperature in AP samples. HBPE-Fc presented an efficient catalytic effect on the thermal degradation of AP and the catalytic reactions were characterized by decreased activation energy and increased rate constant of thermal decomposition. The possible catalytic mechanism was proposed.