In order to enhance the safety and energy of the explosive charge, three new composite charge structures were designed and prepared by 3D printing technology. 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) and 2,4,6-triamino-1,3,5-trinitrobenzene (TATB) were chosen as the main explosive due to high energy density of CL-20 and high safety of TATB. Glycidyl azide polymer binder (GAP) and polyisocyanate (N-100) were used as binders to prepare two energetic formulations TATB/GAP/N-100 and CL-20/GAP/N-100 for 3D printing. Three new structures were constructed by 3D printing based on the two formulations. The effects of the binder contents and printed parameters on microstructure of the energetic charges were studied. Stable charge structure was obtained when the content of the binder, printed speed and the nozzle diameter was 20%, 3 mm·s^-1 and 0.25 μm, respectively. The impact sensitivity of three new structures was studied by GJB772A-1997 method 601.2. The H₅₀ for the axial/radial composite charge structure was about 72.00 cm, which was three times higher than that of raw CL-20.