Abstract: It is crucial to improve the detonation performance of high-energy explosives in the field of energy material. The metal amidoborane (MAB) with high content of hydrogen exhibits excellent chemical stability. Thus, the metal cations and hydrogen can be utilized to improve the thermodynamic properties of high energetic compounds if MAB is doped into the explosives. The crystalline RDX (1,3,5-cyclotrimethylenetriamine) was optimized to analysis the electronic characters. The periodic structure of LAB (Lithium Amidoborane)-doped RDX has been predicted by using Monte-Carlo method to understand the relation between LAB and RDX in solid state. On the basis of their electronic structures, possible reactions between LAB and RDX were designed and analyzed using the theoretical method of BP86/6-311+g (d,p) in Gaussian 09. The results indicated that chemical potentials of LAB doped RDX decreased while the enthalpies of continuous decompositions increased.