The curing kinetics of MDI-based polyurethane elastomers were studied by non-isothermal differential scanning calorimetry (DSC). The kinetic parameters of the reaction system were calculated by the Kissinger method. The changing activation energy was observed by the Flynn−Wall−Ozawa method and the Friedman method. The results of model free fitting showed that the curing reaction could be divided into two stages, showing a change in reaction order when α > 0.45 and a piecewise curing mechanism function of the MDI-based polyurethane elastomers reaction system was deduced by autocatalytic model. The extrapolation method was used to determine the optimum curing conditions for the system, which can accurately describe the curing process. In addition, the optimal curing conditions are when: the constant temperature curing temperature of the system is 81 °C, the curing time is 29 min, and the post-curing temperature is 203 °C.