In this work, Polyquaternium-7 (M550) was utilized as the intermediate layer to strengthen the interface interaction between hexanitrohexaazaisowurtzitane (CL-20) and graphene oxide (GO), and then CL-20/M550-GO (CMG) was prepared through electrostatic self-assembly. The surface morphology and component of CMG were determined, which proved that CL-20 was covered with M550-GO. The thermal measurement showed that the coating of M550-GO can increase the transformation temperature of the crystal form of CL-20. The impact sensitivity and friction sensitivity of CMG was measured by the BAM method, and the results were 35 J and 288 N, respectively. To our best knowledge, this is the best desensitizing effect of CL-20. Meanwhile, the composite presented good compatibility with 3,3-Diazide methyl oxetane and tetrahydrofuran copolyester (PBT) and toluene diisocyanate (TDI), which indicates the potential application of this strategy in a cross-linked propellant system. Excluding the influence of the content and crystal form on the mechanical sensitivity, M550 was ensured to be responsible for the improved desensitizing effect by enhancing the interface interaction between CL-20 and GO. In brief, this work provides an effective strategy to equilibrium between safety and energy properties of the explosive.