Studies on the thermal decompositions of diamyl peroxide (DAPO), dicumyl peroxide (DCPO), and tert-butyl cumyl peroxide (TBCP) were conducted by DSC. Heat of decomposition, exothermic onset point, and chemical kinetics were determined and compared to those data of di-tert-butyl peroxide (DTBP), a model compound for studying thermokinetics of organic peroxide and standardization of a calorimeter. Similarities and differences of decomposition mechanisms between these organic peroxides were proposed and verified. Kinetics on decomposition of uni-molecular reaction via these similar alkoxyl radials accompanying beta C-C bond scission were discussed and compared to the results from ab initio calculations. The ranking of thermal stability on dialkyl peroxides is determined to be in the following sequence: DCPO < TBCP < DAPO < DTBP. This rate-determining step in thermal decomposition of dialkyl peroxides possessed an average eigenvalue of log A at about 13.1 +/- A 1.2. Activation energy on the thermal decomposition of these peroxides was calculated to be 139.5 +/- A 14.4 kJ mol(-1).