Theoretical methods play significant parts in design and exploitation of advanced energetic materials. In this review, some important problems in the theoretical design of energetic materials in our study were introduced in detail, including evaluating the densities, heats of formation (HOFs), thermal decomposition mechanisms and detonation properties of usual energetic compounds. It was suggested that the combined ab initio MD and ab intio MO study can successfully revealed the dissociation mechanisms for some simple hydronitrogen compounds. Additionally, the interface interactions of the incompatible energetic copolymer blends in the presence of block copolymers and plasticizers were discussed. And the effect of nanorods on the interface of immiscible A/B homopolymer blends was also indicated. Results show that Dissipative particle dynamics (DPD) are useful analysis tools for studying the self-assembly of energetic polymers and can give physical insight into the problem. The calculation of the above properties may provide useful information for the molecular design of novel high energetic density materials.