In order to improve the safety performance of hexanitrohexaazaisowurtzitane （CL-20）， the CL-20 with self-assembled stacking structures were prepared by the solvent-nonsolvent method using nitrified graphene （NG） as a crystallization inducer. The morphologies， structures， and thermal properties of the stacking structure CL-20 were characterized by field emission scanning electron microscopy （FE-SEM）， X-ray diffraction （XRD）， fourier transform infrared spectroscopy （FT-IR）， and synchronous thermal analyzer （DSC-TG） respectively， and their mechanical sensitivities were tested and analyzed. The results show that under the induction of different content of NG， CL-20 recrystallizes into square flake crystals， and self-assembles and stacks into petal-shaped， spiral-shaped， tower-shaped， and other structures. During the formation of the self-assembled stacking CL-20， the induction effects of NG are reflected in the adsorption effect of its sheet layer on CL-20 and the formation of hydrogen bonds between NG′s active functional groups with CL-20. Compared with the raw CL-20， the thermal decomposition temperature of the self-assembled stacking CL-20 is reduced by about 5 ℃， the maximum thermal decomposition enthalpy is increased by about 33%， and the mass loss is increased from 81% to 99%. The prepared self-assembled stacking CL-20 has a significantly lower mechanical sensitivity than that of the raw CL-20. When the NG content is 0.5%， the self-assembled petal CL-20 prepared by NG induction has the lowest impact sensitivity of 6 J.