Nanothermites and high-energy explosives have significantly improved the performance of high-energy composites and have broad application prospects. Therefore, in this study, RDX/F2311/Fe₂O₃/Al composite hollow microspheres were successfully prepared utilizing the electrospray method using F2311 as a binder between components. The results show that the combustion time of the composite hollow microspheres is shortened from 2400 ms to 950 ms, the combustion process is more stable, and the energy release is more concentrated. The H50 of the composite hollow microspheres increased from 14.49 cm to 24.57 cm, the explosion percentage decreased from 84% to 72%, and the sensitivity of the composite samples decreased significantly. This is mainly the result of the combination of homogeneous composition and synergistic reactions. The combustion results show that F2311 as a binder affects the tightness of the contact between the components. By adjusting its content, the combustion time and the intensity of the combustion of the composite microspheres can be adjusted, which provides a feasible direction for its practical application.