To solve the problem of nano-aluminum (nAl) powder easy agglomeration and improve its thermal reaction, nAl was hybrid with adhesive (Viton A, F2602) and oxidizer (Ammonium perchlorate, AP) forming microspheres by electrostatic spray method. The morphology and structure were analyzed by SEM, EDS and XPS. The results showed that the microspheres (diameter ≈ Φ10 ~ 15 µm) were hollow structures formed by winding of fluoropolymer fibers, while AP and nano aluminum particles were embedded on the fibers. By controlling the electric spray process, the well-dispersed AP and nAl nanocrystals were assembled on the fiber. Thermal analysis indicated that the gas phase products decomposed by AP were absorbed by porous microspheres, and part of the heat was stored in polymer fibers, thus promoting the breakdown of the alumina shell and accelerating the pre-ignition reaction. The combustion and laser ignition experiments proved hollow heterogeneous microspheres have excellent thermodynamic properties. The assembled microspheres not only solved the problem of poor rheology caused by the agglomeration of nAl, but also improved the insufficient combustion of nAl and the condensation of products.