We found that the intramolecular dehydration of glycol ether (2-alkoxyethanol or 2-aryloxyethanol) to vinyl ether (alkyl vinyl ether or aryl vinyl ether) occurs when glycol ether is made contacted with metal oxide catalysts in the vapor phase. The catalytic performance of SiO2 catalyst alone was very low. Both the conversion of 2-alkoxyethanol and the selectivity for alkyl vinyl ether was markedly increased by the addition of cesium oxide to SiO2. The high activity and selectivity are considered to be due to the presence of both weak acid sites and weak base sites on the modified SiO2. (c) 2006 Published by Elsevier B.V.