Reactive distillation for the production of methyl tert-butyl ether (MTBE) from methanol (MeOH) and tert-butyl alcohol (TBA) using two types of catalysts, ion exchange resin and heteropoly acid (HPA), has been studied. The reaction was performed in the liquid phase and at the boiling point of the reactant mixture under atmospheric pressure. The reactive distillation was examined with and without pervaporation. An azeotropic mixture or MTBE and MeOH was obtained as a top product. HPA showed higher selectivity than did ion exchange resin. It was found that the pervaporation might be effective in removing water.