Aluminum powder was widely used to improve the energy characteristics of explosives and solid propellants due to its excellent properties， such as high activity， high density， high combustion enthalpy and low oxygen consumption. The transition metal Cu had a good catalytic effect on the combustion of aluminum powder and could make the aluminum powder burn more completely. As a binder component of solid propellant， hydroxy-terminated polybutadiene （HTPB） was beneficial to prevent the oxidation and agglomeration of aluminum particles， accordingly in favor of the press-packing and curing while uniformly coating on the surface of aluminum particles. Using the copper acetylacetonate as copper source， formaldehyde and hydrazine as reducing agent， HTPB/Cu/μAl composite particles were prepared by one-pot liquid phase reduction. The structure and morphology of the samples were characterized by IR， XRD， SEM and EDS. Meanwhile， the catalytic performance of HTPB/Cu/μAl on the decomposition of AP was studied. The results showed that the reduced Cu particles were scattered on the surface of aluminum particles， and HTPB was evenly coating on the surface of Cu/μAl. In the DSC curve of HTPB/Cu/μAl， the oxidation exothermic peak of transition metal Cu and the decomposition exothermic peak of HTPB appeared simultaneously between 150-350 ℃. However， the coating had almost no effect on the oxidation exothermic peak of micron aluminum powder at 550 ℃. The average activation energy of HTPB/Cu/μAl was 287.2 kJ·mol^-1， which was 36.35 kJ·mol^-1 lower than that of μAl （323.55 kJ·mol^-1）. Both of the decomposition peaks of AP at high temperature and low temperature had changes when HTPB/Cu/μAl composites were added. Compared with pure AP， the exothermic decomposition peak at high temperature of HTPB/Cu/μAl/AP was reduced by 127 ℃， indicating that the HTPB/Cu/μAl composites could promote the thermal decomposition behavior of AP.