Compared with start-ups in conventional distillation columns, those in reactive distillation (RD) columns are much more time and energy consuming, and generate a large amount of by-products which are not easy to deal with together. For several years, researchers have been trying out different methods to shorten the time required to lower the cost of the start-up. In this work, a rigorous dynamic model in the ChemCAD simulator is applied to model the start-up process for the esterification of ethyl acetate in a reactive distillation column. In the model, two sets of equations are employed: one for the fill-up and heating stage and the other for the equilibration process which follows. In the fill-up and heating stage, fluctuation curves of the reboiler temperatures with respect to time which are similar to those for conventional distillation columns are observed, while in the equilibration process it is found that the increase of the liquid holdup volume in the condenser reduces the time required to reach steady state for the reactive column and decreases the liquid holdup volume in the reboiler at the equilibrium state. This shows that the liquid holdup volume in the condenser has an important effect on the start-up of reactive distillation columns.