CeB6 powders were prepared by high-temperature self-propagating synthesis (SHS) in which CeO2, B203 and Mg were taken as reactants. The adiabatic temperature and dynamics of SHS reactions were investigated. The SHS reaction products and leached products were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results indicated that the adiabatic temperature of Mg-B2Oa-CeO2 reaction system was rather higher than 1800 K to make the reaction propagate by itself, and the apparent activation energy (Ea) and reaction order (n) of exothermic peak on Mg-BzO3-CeO2 differential scanning calorimetry (DSC) curve were 23.03 kJ/mol and 1.31, respectively. The apparent activation energy was lower, so the reaction occurred easily. The SHS products consisted of MgO, CeB6 and little MgaB2O6. The leached products consisted of single CeB6 phase and its purity was higher than 99.0%, and the average particle sizes of CeB6 were smaller than 150 nm.