To address the issues of incomplete aluminum powder combustion， slow energy release efficiency and prolonged ignition delay， nAl@PVDF@CL-20 composite energetic microspheres were fabricated via electrostatic spray technique. The morphological structure and particle size distribution were optimized by adjusting parameters， including eolvent type， lectric field intensity and sand binder content. Experimental results demonstrated that the uniform microspheres with size distribution of 2.37-2.67 μm and homogeneous component dispersion were achieved using a dimethylformamide/ethyl acetate （DMF/EAC） mixed solvent at the volume ratio of 2∶1， with the PVDF content fixed at 5% and electrode voltage maintained at 14 kV. Concurrently， a crystal phase transition of CL-20 from ɛ-CL-20 to β-CL-20 occurred during atomization and deposition processes due to recrystallization. Furthermore， the adoption of nAl significantly enhanced the energy release efficiency and combustion performance of microspheres. The optimal performance was attained at 40% nAl loading， achieving a maximum equilibrium pressure of 1.17 MPa and a peak pressure rise rate of 6.99×10³ kPa·ms^-1.