Methyl ethyl ketone peroxide (MEKPO) has highly reactive and unstable exothermal features. In recent years, it has caused many thermal explosion and runaway reaction accidents in manufacturing processes. Hydrogen peroxide (H2O2), dimethyl phthalate (DMP), and methyl ethyl ketone (MEK) were applied to manufacture MEKPO. To prevent casualties from runaway reactions and thermal explosion events from occurring, the goal of this study was to simulate a process for an emergency response. Differential scanning calorimetry (DSC) was employed to integrate thermal hazard development. Results indicated that MEKPO decomposed at lower temperature (30–40°C) and exploded on exponential development. Temperature of no return (TNR), time to maximum rate (TMR), self-accelerating decomposition temperature (SADT), maximum of temperature (Tmax), etc., were necessary and useful to study emergency response procedure in terms of industrial applications. In view of loss prevention, corporations with reactive chemicals must have an emergency response plan.