The kinetics of the crosslinking reaction of polydimethylsiloxane (PDMS) was studied by differential scanning calorimeter (DSC). The kinetic parameters of the reaction were calculated from the Kissinger, the Ozawa, the Flynn.Wall.Ozawa, and the Friedman methods. The Chang method was also used to determine reaction order and to compare with other methods. To improve the accuracy, the autocatalytic model and the modified-Chang method were introduced. The theoretical heat generation against temperature curves, calculated by the estimated kinetic parameters, well fit the experimental data, which indicated that the analysis method used in this work was valid. The processing time and temperature was predicted by the direct integration of the kinetic equation with the data from isothermal runs. It would give a valuable guide for the thermal processing of silicone rubber.