Tert–butyl peroxybenzoate (TBPB) is one of the sensitive and hazardous chemicals which have been popularly employed in petrifaction industries in the past. This study attempted to elucidate its unsafe characteristics and thermally sensitive structure so as to help prevent runaway reactions, fires or explosions in the process environment. We employed differential scanning calorimetry (DSC) to assess the kinetic parameters (such as exothermic onset temperature (T0), heat of reaction (ΔH), frequency factor (A)), and the other safety parameters using four different scanning rates (1, 2, 4, and 10℃ min–1) combined with curve–fitting method. The results indicated that TBPB becomes very dangerous during decomposition reactions; the onset temperature and reaction heat were about 100℃ and 1,300 J g–1, respectively. Through this study, TBPB accidents could be reduced to an accepted level with safety parameters under control. According to the findings in the study and the concept of inherent safety, TBPB runaway reactions could be thoroughly prevented in the relevant plants.