The gas phase synthesis of MTBE was studied using three series of zeolites modified by ion-exchange with ammonium fluoride, the parent materials being HY, H-mordenite, and HZSM-5. Modification of zeolites by fluoride-exchange was found to enhance the MTBE synthesis activity for all three types of zeolites without impairing their excellent selectivity to MTBE. The mechanism of activity enhancement by fluoride-modification appears to be related to the formation of extra-lattice Al rather than the presence of fluoride-ions.