The kinetic behavior of preparing diphenyl carbonate by the transesterification of dimethyl carbonate with phenol in a reactive distillation reactor has been explored experimentally and theoretically. The transesterification reaction was described to conform a pseudo-second-order kinetics, and a semi-empirical kinetic model has been derived to explain the kinetic behavior. The model parameters were fitted to experimental data by an improved genetic algorithm. The proposed model was determined to be useful in simulating the rate constant and the mole fraction of components, which agreed well with the experimental data for different operating temperatures and catalyst concentrations.