Aluminum powder is the main metal fuel in composite propellants, and upgrading the proportion of aluminum powder loaded in solid propellants is currently one of the most effective means of increasing propellant energy. Nonetheless, the substantial disparity in boiling points between the core aluminum particles and the alumina layer enveloping their surfaces often results in reduced reactivity, inadequate combustion, and combustion agglomeration during the combustion process of the aluminum powder. Herein, copper pentafluorobenzoate (CuPF) interfacial layer was established on the surface of aluminum powder through the self-assembly coordination reaction between pentafluorobenzoic acid and copper ions, and Al-CuPF energy microspheres were successfully prepared. A comprehensive examination was carried out to scrutinize the surface morphology, elemental composition, and distribution of the Al-CuPF energy microspheres. Furthermore, meticulous studies were conducted on the ignition and combustion properties of these Al-CuPF energy microspheres under various atmospheric conditions. It was found that the Al-CuPF interfacial layer within the Al-CuPF energy microspheres plays a pivotal role in enhancing ignition initiation and acting as a catalyst to facilitate the more efficient combustion of aluminum powder. Moreover, the combustion behavior of Al-CuPF energy microspheres when integrated into composite propellants has been exhaustively researched. Notably, composite propellants incorporating Al-CuPF energy microspheres exhibit heightened burning temperatures and an increased burning rate. Additionally, the combustion and agglomeration dynamics of Al-CuPF energy microspheres on the propellant burning surface were meticulously documented using a high-speed camera. The findings revealed that Al-CuPF energy microspheres spend a significantly shorter duration on the propellant burning surface and notably mitigate the occurrence of aluminum agglomeration issues thereon. This research contributes fresh insights into the application of innovative aluminum-based fuels within the realm of composite propellants.