Abstract: Glycol ethers were synthesized via the reaction between ethanol and 1,2-epoxypropane using calcined Mg/Al layered double hydroxides(CLDH) as catalysts. The influence of pore structure and composition of CLDH on the catalytic activity and product distribution of glycol ethers is studied systematically. In addition, the catalytic activity of CLDH as a function of times of reuse is also investigated. The result showed that the catalytic activity increased with the increase in the basicity and specific surface area of CLDH. Furthermore, glycol ether oligomers distribution varied with the pore size distribution of CLDH catalysts.