Abstract: α-FeOOH nanorods were prepared by hydrothermal method with FeSO₄·7H₂O and CH₃COONa·3H₂O as raw materials, and then α-Fe₂O₃ nanorods were obtained by sintering the synthesized α-FeOOH nanorods at 250 ℃ for 2 h. The catalytic performance of α-FeOOH and α-Fe₂O₃ nanorods on the thermal decomposition of ammonium perchlorate was investigated by differential thermal and thermogravimetric analysis. The results show that pure phase α-FeOOH nanorods with an average diameter of 18 nm were prepared by hydrothermal reaction at 100 ℃ for 6 h. After sintering the synthesized α-FeOOH nanorods at 250 ℃ for 2 h, the pure hexagonal phase α-Fe₂O₃ nanorods with an average diameter of 16 nm were obtained. The catalytic effect of α-Fe₂O₃ and α-FeOOH nanorods on the thermal decomposition of ammonium perchlorate was significant; after adding 2 mass% α-Fe₂O₃ nanorods and 2 mass% α-FeOOH nanorods, the end decomposition temperature of ammonium perchlorate decreased by 40 ℃ and 54 ℃, and the high temperature decomposition peak temperature decreased by 51.1 ℃ and 61.6 ℃, respectively. When the mass fraction of α-Fe₂O₃ nanorods reached 10%, the high temperature decomposition peak temperature was reduced by about 90.9 ℃.