An efficient solid Lewis acid, has been synthesized by loading cerium triflate (7 wt%) on the acid activated fly ash with high silica content (81%). The physico-chemical properties of synthesized fly ash-supported cerium triflate catalyst (CFT) were monitored by XRD, FT-IR spectroscopy, FT-IR spectroscopy of the ammonia adsorbed catalyst, SEM-EDAX, TEM, Flame Atomic Absorption Spectrophotometer and TG-DTA study. The increased concentration of silica surface hydroxyl groups on activated fly ash have a major influence on the loading of cerium triflate. The catalytic activity of the catalyst CFT was tested in the acylation of veratrole using acetic anhydride as the acylating agent. The proposed model structure of CFT shows that the triflate species withdraws the electron density from the surface cerium making it electron deficit and generate Lewis acidity on the surface of fly ash as confirmed by NH(3) adsorbed FT-IR spectrum. The activity data indicate that this heterogeneous catalyst is very active, corresponding to high conversion (88%) of veratrole to 3,4-dimethoxyacetophenone. The catalyst could be easily recovered and reused giving similar conversion up to three reaction cycles indicating its stability under experimental conditions. Thus fly ash-supported cerium triflate is a novel and efficient catalyst and is a promising way of bulk utilization of waste fly ash by developing cost effective catalyst system for industrially important Friedel-Crafts acylation reactions. (C) 2010 Elsevier Ltd. All rights reserved.