1, 1′-Dihydroxy-5, 5′-bitetrazole compound is hot spot of high-energy insensitive materials in recent years. To explore the thermal safety of these kinds of compounds, the thermal decomposition processes of 1, 1′-dihydroxy-5, 5′-bitetrazole cobalt salt (1, 1′-BTOCo), copper salt (1, 1′-BTOCu) and lead salt (1, 1′-BTOPb) were studied by differential scanning calorimetry (DSC) and thermogravimetry (TG) at heating rates of 5, 10, 15, and 20 K·min^-1, respectively. The apparent activation energy (E_K and E_O) and pre-exponential factor (A_K) for thermal decomposition reaction were calculated by Kissinger′s and Ozawa′s method, respectively. The kinetic parameters and mechanism functions of thermal decomposition were obtained. Results show that for 1, 1′-BTOCo, E_K=162.35 kJ·mol^-1, A_K=1.83×10¹⁵ s^-1, self-accelerating decomposition temperature T_SADT =534.46 K, critical temperature of thermal explosion T_bpo=542.22 K; for 1, 1′-BTOCu, E_K=217.95 kJ·mol^-1, A_K=12.58×10²⁰ s^-1, T_SADT =527.56 K, T_bpo=539.11 K; for 1, 1′-BTOPb, E_K=223.52 kJ·mol^-1, A_K=4.24×10²⁰ s^-1, T_SADT =525.87 K, T_bpo=580.00 K.