By combining a recent proposed elaborately simulated decomposition kinetic method for organic peroxide with the Semenov model of thermal explosion, the self-accelerating decomposition temperatures (SADTs) of organic peroxides were predicted. The heat generation equation is based on a reaction rate equation, which was expressed by differentiation of a fractional conversion equation with respect to time. The kinetic parameters involved in the calculation are the contribution fraction phi(i), the end point temperature T-di, and the reaction temperature range parameter K-Ti, which are directly determined by observing the thermal behavior of peroxides under non-isothermal decomposition condition. The non-isothermal decomposition behaviors of eight organic peroxides were measured by the heat flux calorimeter C80D. By using the experimental results and the developed method, the no return temperature and the self-accelerating decomposition temperatures of these substances in UN 25 kg test and 0.5 liter Dewar test were predicted. The predicted SADTs were in agreement with the literature values. (C) 2003 Elsevier Ltd. All rights reserved.