Three novel rare-earth,nitrogen-rich and oxygen heterocyclic supramolecular complexes,namely[Nd(BTF)2(H2O)5]n,[Sm(BTF)2(H2O)5]n,and[Eu(BTF)2(H2O)5]n,were synthesized.A single crystal was ob-tained by the solvent evaporation method,and the structure and coordination mode of metal complexes were determined by single crystal X-ray diffraction.Results show that the supramolecular complexes contain many hydrogen bonds and thus have good thermal stability (Tdec ＞ 540 K).The thermal decomposition of ammonium perchlorate (AP) catalyzed by the complexes was investigated by differ-ential thermal analysis,which reveals a pre-eminent catalytic effect on AP.The high temperature decomposition peak of AP can be advanced by nearly 90 K at the amount of added complexes of 10 wt％,and the activation energy of AP descent range is from 70 to 150 kJ/mol.The other properties were fully characterized through elemental analysis and Fourier transform infrared spectroscopy.