An interesting Cu-Co/GO composite with special high organic content was accidentally fabricated for the first time via a one-pot solvothermal method in the mixed solvent of isopropanol and glycerol. The Cu-Co/GO composite was calcined separately in three different atmospheres (air, nitrogen, and argon) and further investigated by a series of characterization techniques. The results indicate that the spinel phase nano-CuCo2O4 composite, nanometal oxides (CuO and CoO), and nanometal mixture of Cu and Co were unexpectedly formed after calcination in air, N-2, and Ar atmospheres, respectively, and the possible reaction mechanism was discussed. The specific mass losses of the Cu-Co/GO composite calcined in air, N-2, and Ar atmospheres were 28.14 %, 21.68 %, and 23.76 %, respectively. The catalytic decomposition performances of the as-prepared samples for cyclotrimethylenetrinitramine (RDX) and the mixture of nitrocellulose (NC) and RDX (NC + RDX) were investigated and compared via DSC method, and the results demonstrate that Cu-Co/GO composites obviously decrease the thermal decomposition temperature of RDX from 242.3 to 236.5 (before calcination), 238.6 (air), 235.8 (N-2), and 228.6 degrees C (Ar), respectively. Cu-Co/GO(Ar) composite exhibits the best catalytic decomposition performance among all samples, which makes the decomposition temperature of RDX and NC + RDX decrease by 13.7 and 4.9 degrees C and the apparent activation energy of decomposition for RDX decrease by 110.1 kJ/mol. The enhanced catalytic performance of Cu-Co/GO(Ar) composite could be attributed to the smaller particle size, better crystallinity, and specific well-dispersed metal atoms, whereas the Cu-Co/GO(air) composite after air calcination presents a bad catalytic performance due to the removal of GO.