Di-tert-butyl peroxide (DTBP) has been widely employed in chemical industries. Unfortunately, many serious explosions and fires have occurred during the manufacturing process, storage, and transportation of organic peroxides. This study investigated the thermokinetic parameters by isothermal-kinetic and nonisothermal-kinetic simulation, using differential scanning calorimetry (DSC) tests. Green thermal analysis technology was applied to assess the kinetic parameters, such as the kinetic model, frequency factor (ln k0), activation energy (Ea), reaction order, heat of reaction (ΔHd), etc. Comparisons of nonisothermal and isothermal kinetic model simulation led to a beneficial kinetic model of thermal decomposition to predict the thermal hazard of DTBP. Simulations in 0.5 L Dewar vessel and 25 kg barrel commercial package in liquid thermal explosion models were performed and compared to the results in the literature. From the results, we determined the DTBP of the optimal conditions to avoid violent runaway reactions during the storage and transportation. This study established the features of green thermal analysis technology that could be executed as a reduction of energy potential and storage conditions in view of loss prevention.