Micro-nano composite energetic materials have attracted much attention due to their excellent properties and have broad application prospects in the fields of explosives and propellants. The electrostatic spray method， as an emerging composite material preparation technology， has a significant impact on the assembly and energy release regulation of energetic materials. To address the issues of insufficient combustion of micro aluminum powder， low energy release efficiency， and long ignition delay， the electrostatic spray method was used to successfully prepare uniformly mixed hexanitrohexacyclohexylazomethine/polyvinylidene fluoride/nanometer aluminum （CL-20/PVDF/nAl） based composite energetic microspheres. These microspheres were further modified with ferric oxide （Fe₂O₃） and reduced graphene oxide （rGO）. The results showed that the samples prepared by the electrostatic spray method had a regular morphology， uniform size， high sphericality， and a particle size of approximately 1-7 μm. Compared with the physical mixture samples， microspheres exhibit superior thermal and combustion properties. Additionally， the addition of oxidant Fe₂O₃ and catalyst rGO can significantly improve the energy release efficiency and combustion performance of the microspheres， and when the content reaches 20% and 4% respectively， the shortest combustion time is 7 ms， the minimum ignition delay time is 0.13 s， the maximum equilibrium pressure is 2.17 MPa， and the maximum pressure rise rate is 1.63×104 kPa·ms^-1.