To study the thermal decomposition of dihydroxylammonium 5,5′-bistetrazole-1,1"-diolate (TKX-50), thermal decomposition experiments such as thermogravimetry and differential scanning calorimetry were carried out, respectively. Meanwhile, MATLAB software was employed to decouple the overlapping parts and the Málek method was used to study the kinetics of the thermal decomposition of TKX-50. The results show that the thermal decomposition process of TKX-50 is divided into two stages. The complete thermal decomposition curves of the two stages are obtained by MATLAB software, and the basic parameters such as T_onset, T_p, and ΔH are acquired at different heating rates. The thermal decomposition of TKX-50 follows the autocatalytic reaction model, and the kinetic parameters including activation energy, pre-exponential factor and kinetic model are obtained, respectively. For the first stage,E_a=174.99 kJ∙mol^-1,lnA=40.75,f(α)=α^0.917(1-α)^0.509， for the second stage,E_a=149.60 kJ∙mol^-1,lnA=31.84,f(α)=α^0.357(1-α)^0.117.