Boron has a promising application in the field of propellants due to its high calorific value. However, the difficulty of ignition and the poor combustion efficiency of boron (B) have severely limited its efficient application. In response to this issue, this paper proposes to improve the ignition and combustion performance of micron-sized boron by the Polyvinylidene Fluoride (PVDF) coating. The effect of PVDF content on the B combustion performance was systematically studied using a Thermogravimetry-Differential Scanning Calorimetry (TG-DSC), a Transmission Electron Microscope (TEM), an X-Ray Diffractometer (XRD), a laser Particle Size Analyzer (PSA), and a high-speed camera. The results show that PVDF can significantly reduce the initial oxidation temperature of B powder and increase its reaction heat. When the PVDF content is 23wt%, the reaction heat and the combustion intensity of B powder reach the maximum and are significantly higher than those of the uncoated B powder. Moreover, the fluorination reaction that occurs during the combustion process not only can effectively shorten the combustion time of B powder, but also has a positive effect on its flame intensity and propagation speed, and it significantly reduces B particle agglomeration, which improves the combustion efficiency significantly. This study lays the foundation for the application of PVDF modified B in B-based solid propellants.