A new energetic material dirubidium 5, 5′-bis (tetrazole-1-oxide) (BTORb) was synthesized by using 1H, 1′H-5, 5′-bistetrazole-1, 1′-diolate (BTO) as the original material. The monocrystal of target salt was first cultivated by the method of gradual evaporation, and the single crystal structure was menstruated by single X-ray diffraction. It is found that the Rb⁺ and BTO^2- formed a dissymmetrical structure. In different layers, they are alternately arranged and connected with each other, forming a three-dimensional reticular structure. Its thermal decomposition behavior was investigated through DSC and TG-DTG technologies, indicating a good thermal stability with a decomposition temperature beginning at 292 ℃. Its kinetic parameters of non-isothermal reaction was calculated by Kissinger and Ozawa methods with the equation of Arrhenius is lnk=13.51-186.3×10³/RT. Its standard heat of formation was calculated with the result of 274.91 kJ·mol^-1. Its critical temperature of thermal explosion T_b is 356.7 ℃, indicating that the salt has a good thermal stability. The impact sensitivity (H₅₀) of BTORb is 34.8 cm, with the drop hammer of 800 g. The friction sensitivity is 36%, under the condition of 70°, 1.23 MPa. The 50% fire energy of electrostatic spark sensitivity is 0.34 J.