The benzoyl peroxide (BPO) is widely used in the chemical industry. Many catastrophes have been caused by its thermal instability or reactive incompatibility in storage or thermal decomposition reaction. Thus. its hazard characteristics have to be clearly identified. First of all, the differential scanning calorimeter (DSC) is used to measure the heat of decomposition reaction, which can contribute to understanding the reaction characteristics of benzoyl peroxide. The accelerating rate calorimeter (ARC) is used to measure the rates of temperature and pressure rises of decomposition reaction, and then the kinetics parameters are estimated. Furthermore, the MIKE 3 apparatus and the 20-1-Apparatus are used to measure and analyze the dust explosion characteristics of benzoyl peroxide under room temperature and atmospheric pressure. Finally, Semenov's thermal explosion theory is applied to investigate the critical runaway condition and the stability criterion of decomposition reaction, and to build the relationship of critical temperature, convective heat transfer coefficient, heat transfer surface area and ambient temperature. These results contribute to improving the safety in the reaction, transportation and storage processes of benzoyl peroxide. (C) 2008 Elsevier B.V. All rights reserved.