In order to improve the thermal decomposition performance of AP,based on the intrinsic positive charge and amino group of polyethyleneimine(PEI),the AP/PEI/Cu(ClO4)2 coated sample was prepared by adsorbing copper metal catalyst on the surface of AP while electrostatic self-assembly coating with negative charge AP,and its thermal decomposition behavior was studied by thermal analysis technology.The morphology and structure of AP/PEI/Cu(ClO4)2 coated samples were charac-terized by SEM,XPS,XRD,IR,ICP-OES,and Zeta potential.The results show that compared with raw AP,the high temper-ature decomposition peak temperature of AP/PEI/Cu(ClO4)2 coated sample is reduced by 94.2 ℃,and the apparent heat re-lease is increased by 512.91 J/g,which confirmed that PEI/Cu(ClO4)2 has a good catalytic effect on the thermal decomposi-tion of AP.The addition of PEI can enhance the interfacial interaction between metal catalyst and AP,making the catalyst more evenly distributed on the surface of AP,promoting the better catalytic effect of metal catalyst on the thermal decomposition.