The invention relates to a process for refining glycol dimethyl ether by using a pervaporation method. The process comprises the following steps: neutralizing Williamson synthesized glycol dimethyl ether mother solution, and then, settling to obtain crude glycol dimethyl ether; separating the crude glycol dimethyl ether through a rectifying tower, discharging a glycol dimethyl ether and water azeotrope from the top of the tower, condensing, and then, collecting the glycol dimethyl ether and water azeotrope into an intermediate tank; discharging part of water and ethylene glycol monomethyl ether from the bottom of the tower; delivering the glycol dimethyl ether and water azeotrope to a preheater, and then, enabling the glycol dimethyl ether and water azeotrope to enter an evaporator, wherein the glycol dimethyl ether and water azeotrope is collected in the intermediate tank; enabling water-contained glycol dimethyl ether to enter a pervaporation membrane separator, wherein the water-contained glycol dimethyl ether is evaporated from the evaporator; condensing penetrating materials through a penetrating liquid condenser, then, enabling the penetrating materials to enter a penetrating liquid tank, further, returning the penetrating liquid to the rectifying tower to carry out recovery treatment, thus obtaining high-purity glycol dimethyl ether at the interception side of the pervaporation membrane separator; and, preheating through the preheater, condensing through a finished product condenser, and then, enabling the high-purity glycol dimethyl ether to enter a product tank. The process is simple in technological process, low in equipment investment as well as high in energy utilization ratio and recovery rate.