Effects of variations sulfur/accelerator ratio on cross-linking and thermal degradation behavior of NR/CR rubber compounds were studied using both dynamic DSC and non-isothermal TGA. DSC thermograms of the given samples were obtained with several different heating rates, and after cross-liked in DSC, TGA thermograms with the same samples also obtained. Kissinger analysis was applied to assess the activation energies for the cross-linking and thermal decomposition processes. Results showed that the formation and thermal decomposition reaction of the samples occurred in the overall temperature range of 120~180 ℃ and 350~450 ℃, respectively, exhibiting that data could be well-fittable by Kissinger method. Furthermore, formation activation energy by DSC was estimated as 83.0±5.0 kJ/mol, which was much smaller than that of degradation by TGA, 147.0±2.0 kJ/mol. From these results, it was considered that, although variations of sulfur/accelerator ratio in the present experiments affected little on the formation mechanism and/or thermal degradation, they could play roles as the catalysts which lower the activation energy of formation. Because of stabilization after formation reaction, however, they have no more effects on the lowering the activation energy, showing higher values when decomposition, caused by main-chain scissions.