A new energetic copper complex of dinitroacetonitrile (DNANT), [Cu(NH3)4](DNANT)2, was first synthesized through an unexpected reaction. The thermal decomposition of [Cu(NH3)4](DNANT)2 was studied with DSC and TG/DTG methods. The gas products were analyzed through a TG-FTIR-MS method. The nonisothermal kinetic equation of the exothermic process is dα/dT = 10(10.92)/β4(1 - α)[-ln(1 - α)](3/4) exp(-1.298 × 10(5)/RT). The self-accelerating decomposition temperature and critical temperature of thermal explosion are 217.9 and 221.0 °C. The specific heat capacity of [Cu(NH3)4](DNANT)2 was determined with a micro-DSC method, and the molar heat capacity is 512.6 J mol(-1) K(-1) at 25 °C. Adiabatic time-to-explosion of Cu(NH3)4(DNANT)2 was also calculated to be about 137 s.