The applicability of reactive distillation for esterification of glycerol with acetic acid in the presence of Amberlyst-15 as catalyst and ethylene dichloride as an entrainer is evaluated through experiments and simulation. The reaction is studied in both semibatch and continuous reactive distillation systems. The effect of different parameters such as entrainer amount, catalyst loading, and reboiler duty is studied. The results indicate that entrainer-based semibatch reactive distillation can enhance the selectivity toward triacetin to about 100%, which is much greater than that offered by any conventional reactor with stoichiometric mole ratio of reactants. Simulations for both sernibatch and continuous reactive distillation are performed, and results agree reasonably well with those obtained by experiments. The best possible design and operating parameters are obtained through detailed simulation using an experimentally validated model. A column configuration is recommended for a continuous process.