A new energetic iron-oxygen cluster， ［Fe₂^Ⅲ（μ₂-CH₃O）（μ₃-OH）（μ₂-O）（BODTO^2-）（H₂O）］₄ （1）， was synthesized by solvothermal method using 5，5"-｛［3，3"-bis（1，2，4-oxadiazole）］-5，5"-yl｝-bis（1-hydroxytetrazole） as ligand. The structure and thermal stability of compound 1 were studied by single-crystal X-ray diffraction， differential scanning calorimetry and thermogravimetric analysis. The catalytic performance of compound 1 on the thermal decomposition of ammonium perchlorate （AP） was also investigated by differential thermal analyzer. Compound 1 crystallizes in cubic I-43d space group with a density of 1.506 g·cm^-3. In the crystal structure， the nearby Fe³⁺ cations are interconnected to each other by bridging oxygen atoms. Through those connections， the iron（Ⅲ） cluster cages are formed. The peak thermal decomposition temperatures of compound 1 are 513.9， 617.6 K and 669.4 K， respectively. The detonation velocity and detonation pressure of compound 1 are 6.94 km·s^-1 and 19.09 GPa， respectively. In addition， the impact sensitivity and friction sensitivity of compound 1 are 15 J and 360 N， respectively. After adding 10% compound 1 to AP， the high temperature decomposition temperature of AP decreases by 65 K， and the decomposition activation energy decreases by 82.2 kJ·mol^-1， demonstrating the high catalytic activity of compound 1 for the thermal decomposition of AP and the great potential of compound 1 for application in energetic combustion catalysts.