The Ferrier glucosylation of alcohols with 3,4,6-tri-O-acetyl-D-glucal has been investigated with several metal nitrates and the optimal catalyst is bismuth nitrate pentahydrate (BNP). Good yields of pseudoglycals were also obtained with ferric nitrate nonahydrate (INN), heightening the catalyst dosage (50 mol%) being required however. The BNP-mediated reactions showed remarkable solvent dependency and in the optimal protocol, the amount of BNP as low as 10 mol% was effective, furnishing excellent yields of O-glucosides with good anomeric selectivity in acetonitrile. A comparison of BNP and INN in terms of yields and selectivity of the product has been made. In comparison to the reactions in acetonitrile, the catalytic ability of BNP was found to enhance drastically in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF6]. (c) 2005 Elsevier B.V. All rights reserved.