Theoretical calculation was used to investigate the molecular structures and orbitals of five BEBA molecules. Relative to trimethyl borate, the lowest unoccupied molecular orbital (LUMO) images of five BEBAs (1-5) molecules show that the orbitals do not appear around borate groups, and their energy levels of those unoccupied molecular orbitals around boron atom are higher. Molecular dynamics simulation was performed to investigate the interaction between title borate esters and RDX(210) as well as RDX(210) crystal faces. An obvious binding selectivity of these borate esters on RDX crystal surfaces is found. The binding energies of RDX(200)/BEBAs are higher than that of RDX(210)/BEBA(1-5). The theoretical evaluation for the binding performances of BEBA_1 and BEBA_2 with RDX are good enough, whereas the binding performances of RDX(210)/BEBA_5 and RDX(200)/BEBA_5 are contrary. It is speculated that less oxygen content of the most superficial surface of RDX(200) is benefit of forming induced effects between carbonyl of BEBA_5 and NO₂ in RDX. Such a strong combination between them offsets or even compensates the lowering of binding energy caused by depletion of nitrogen′s negative charge on amines.