As a new high energy explosive, it is particularly crucial for HNIW (2, 4, 6, 8, 10, 12-hexanitrohexaazaiso-wurtzitane) to modify the comprehensive performance especially under the modern battlefield environment. Unlike the ordinary modifying method such as recrystallization and polymer coating, the formation of HNIW cocrystal with low sensitivity micromolecule explosive can achieve the modification from the inner composition and the invariant inherent molecular structure. Consequently, HNIW/DNT(dinitrotoluene) cocrystal was prepared by slow solvent evaporation method at room temperature. Using X-ray diffraction, Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy analysis, the crystal structure, intermolecular non-bonding interactions and comprehensive properties of the cocrystal were characterized and analyzed. The characterization results showed that a new sharp peak appeared in the co-crystal PXRD diffraction pattern, which indicated that the cocrystal was a totally new non-solvated crystalline phase rather than the crystal transformation product. In fourier transform infrared spectroscopy and Raman spectroscopy, the peak shifts and peak height, peak width of some characteristic absorption peak changed, which confirmed the formation of HNIW/DNT cocrystal. And the intermolecular interactions was mainly the result of intermolecular interactions between HNIW and DNT molecular.