Mechanically mixed and electrostatic sprayed RDX/NC/AP/Al composite explosive using nitrocellulost （NC） as binder， ammonium perchlorate （AP） as oxidant， cyclotrimethyltrnitramine （RDX） and nano aluminum powder （Al） as combustion agent were prepared based on zero oxygen balance. The morphology， structure， thermal properties， combustion process and mechanical sensitivity of the different samples were analyzed by the scanning electron microscopy （SEM）， the Fourier transform infrared spectroscopy（FT-IR）， thermogravimetric differential scanning calorimeter （TG-DSC）， mechanical sensitivity and high-speed photography. The component（NC， RDX， AP and Al） in RDX/NC/AP/Al composite explosives obtained by both method are physical composite. However， the microstructure of mechanically mixed RDX/NC/AP/Al demonstrated in spheres and the electrostatic sprayed samples are microspheres. The mass loss process of RDX/NC/AP/Al composite explosive obtained by two methods contained two stages （200-210 ℃ and 250-350 ℃）. The first stage is the decomposition of part of RDX and AP， while the second stage is the decomposition of the remaining RDX and NC. Compared with the mechanical mixed samples， the activation energy and the critical temperature of thermal explosion of electrostatic sprayed RDX/NC/AP/Al increased by 41.25 kJ·mol^-1 and 4.09 K， respectively. Besides， the mechanical sensitivity is reduced， and the combustion rate is also improved.