tert-Butyl hydroperoxide (TBHP, 70 mass %), which is a solution of liquid peroxide, has been widely employed in the chemical industry as a polymerization initiator. The smart technology for predicting the mechanism of thermal decomposition and the inhibitive or hazardous reaction of TBHP by different calorimetric tests involves using differential scanning calorimetry (DSC) nonisothermal tests versus DSC isothermal tests and vent sizing package 2 (VSP2) adiabatic tests versus DSC nonisothermal tests, respectively, for further understanding how to extinguish organic peroxide accidents under fire scenario or runaway reaction in a chemical plant. Meanwhile, TBHP mixed with inhibitive and hazardous materials, such as various protic acids to help prevent runaway reactions, was applied on fires or explosions in the fire system. The results could be available to fire-related agencies as a reference application. The fire extinguishing system must be well-designed to decrease the degree of hazard.