Boron nanoparticles, with their remarkably high gravimetric and volumetric calorific values, emerge as the most promising fuel in energetic fields. However, challenges such as susceptibility to oxidation, high ignition temperature, and low combustion efficiency have constrained their further applications. In this study, we fabricated high explosives based nano-boron microspheres with uniform size using the electrostatic spray method, in which the boron nanoparticles and high explosives (CL-20 or PETN) are closely bonded together by fluorinated polymer (F₂₆₀₂) and evenly distributed. The results indicated that the microspheres exhibited high sphericity and showed an enhanced antioxidant capability. The addition of high-energy explosives not only reduced the thermal oxidation temperature of nano-boron powder within the microspheres but also significantly enhanced the pressurization rate. Additionally, the microspheres with added high-energy explosives released more energy during the combustion process. Compared to physically mixed samples, electrostatically sprayed microspheres with a uniform microstructure still exhibited higher reactivity. Therefore, the design and synthesis of microspheres with controllable structures using the electrostatic spray method show promising application prospects.