Thermo-decomposition performances of RDX and corresponding HMX-doping samples were studied comprehensively through microcalorimetric experiments. Thermo-decomposition curves and parameters without the influence of melting phase transition were simulated via decoupling peak separation method through AKTS software. The thermo-decomposition activation energies (E_a) of all the samples were calculated via Kissinger, Friedman and Ozawa methods, respectively. The results showed that RDX was belonging to melt decomposition materials. Its melting peak temperature was in the region of 201.07~208.05 ℃, while its decomposition peak temperature was in the range of 207.99~232.76 ℃. Its thermo-decomposition Ea value was 167.7 kJ·mol^-1 calculated via Kissinger method which was consistent well with the values which calculated via Friedman and Ozawa methods, respectively. The Ea values were further confirmed by AKTS simulated result. On the other hand, the melting and decomposition peak temperatures of HMX-doping samples were decreased with the doping of HMX. The precise decreased values were 8.63, 8.32, 9.70, 8.57 ℃ and 6.50 ℃ for melting peak temperatures and 1.14, 2.01, 2.58, 3.53 ℃ and 3.47 ℃ for decomposition peak temperatures with the RDX:HMX ratios of 9∶1, 8∶2, 7∶3, 6∶4, 5∶5, respectively. Notably, the thermo-decomposition E_a values of HMX-doping samples were also decreased with the increase content of HMX. The corresponding E_a values are 149.78, 151.40, 149.78, 132.93 kJ·mol^-1 and 132.93 kJ·mol^-1, respectively.