A novel and stereocontrolled glycosidation of 3,4,6-tri-O-acetyl-D-glucal with various alcohols to give the corresponding 2,3-unsaturated glycopyranosides using [bmim]Cl-1.5FeCl(3) based ionic liquid is presented. This ionic liquid has proved to be an efficient reaction medium, playing a dual role of a catalyst as well as of a solvent. Salient features of this simple methodology include non-hazardous reaction conditions, good yields in short reaction times and high anomeric selectivity. (C) 2004 Elsevier B.V. All rights reserved.