This study demonstrates the thermal actions of tert-butyl peroxybenzoate (TBPB) which is widely used in the plastic and rubber industries. The thermodynamic and kinetic analysis were performed on the basis of dynamic and adiabatic calorimetric applications which had been accepted as good assistants for investigating materials’ thermal decomposition. In essence, TBPB is reactive and exothermically unstable. Differential scanning calorimetry (DSC) and accelerating rate calorimeter (ARC) were employed to supply basic data and safety index. Experiments were taken under different scanning rates as well as various sample mass. The temperature and pressure curves of TBPB during decomposition were recorded. Based on the significant parameters calculated, self-accelerating decomposition temperature (SADT) of TBPB worked out was 50°C.