This study focused on green technology to replace the easy-to-make-mistake methods of predicting kinetics and the consumption energy of the transitional self-accelerating decomposition temperature (SADT) tests, using simply thermal analysis combined with kinetic and thermal hazard simulation. Organic peroxides (OPs) have been widely employed in the chemical industry as a polymerization initiator, cross-linking or hardening agent. We investigated the thermokinetic parameters of tert-butyl peroxy-2-ethyl hexanoate (TBPO) with various calorimetric tests by differential scanning calorimetry (DSC) and thermal activity monitor III (TAM III). Comparisons of two calorimetric tests were conducted for simulation approach, which can predict the beneficial kinetics of thermal decomposition, and then we determined the thermal hazard of TBPO. Therefore, this study used green technology to predict the safety parameters of organic peroxide, which also can be applied to optimize reactor design, to improve feeding safety, and to correct process mistakes for other chemicals.