Micro-sized aluminum (m-Al) has been widely used in explosives as fuel additives. Unfortunately, m-Al displays relatively long ignition delay and insufficient combustion characteristics, thus the energy can hardly be fully released in aluminized explosives. In this work, fluoropolymer coated m-Al composites were prepared by solvent evaporation method. SEM images reveal that fluoropolymer is uniformly distributed on the surface of m-Al, and most of the as-prepared particles are microspheres without apparent agglomeration. Thermal behavior results show that the presence of fluoropolymer is beneficial to the oxidation reaction of Al particles. The laser ignition experiments further confirms this conclusion. A small-scale disc acceleration experiment (DAX) was designed to evaluate the metal acceleration ability and detonation performances of CL-20 based explosives containing fluoropolymer coated m-Al composite. And the results indicate that when incorporating the fluoropolymer coated aluminum composites into explosives, the metal acceleration ability and detonation performances can be enhanced. Hopefully, the work of this paper is beneficial to the development of new methods to improve the performances of aluminized explosives.