The thermal properties, electronic structure and detonation performances of 3, 7-bis(nitroimino)-2, 4, 6, 8-tetraazabicyclo[3.3.0]octane were investigated by the TG-DTG-DSC method and density functional theory, respectively. Results show that the thermal decomposition of title compoud is a two-stage process and has an evident exothermic peak at around 320 ℃, and the activation energy and pre-exponential factor of thermal decomposition are 225.80 kJ·mol^-1 and 10^17.71 s^-1, respectively. The critical temperature of thermal explosion is 600.25 K, and entropy of activation 80.81 J·mol^-1·k^-1, enthalpy of activation 220.92 kJ·mol^-1, free energy of activation 173.87 kJ·mol^-1, detonation pressure 34.34 GPa, detonation velocity 8.70 km·s^-1, indicating that it can be used as a potential candidate of high-energy and stable energetic material.