A new type of membrane microreactor was designed and set up. The intensification of miniaturization for the coupling process of pervaporation and reaction was investigated. The esterification reaction was chosen as a model reaction. The influences of the content of catalyst and temperature on the reaction were examined in the membrane microreactor with and without pervaporation. The results showed that conversion rate rose from 13.6% to 54% with pervaporation under the conditions of 65℃ and residence time of 60 min. The large specific surface area and short diffusion distance of the membrane microreactor could promote the removal of water and intensify the coupling process of pervaporation and reaction. The conversion rate of esterification was 54.0% in the membrane microreactor and 29.3% in the conventional macro-scale membrane reactor under the conditions of 65℃, residence time 60 min and content of Zr(SO4)2 15%(w). In addition, the deactivation of catalyst could be effectively reduced in the membrane microreactor. Its repeatable utilization was improved.