Catalytic activity of 14 types of metal ion-exchanged montmorillonite K-10 clay (Mn+-mont) is tested for the acetylation of cyclohexanol with acetic anhydride at room temperature. The activity increases with an increase in the charge/radius ratio of exchanged cation. The activity of Fe3+-mont is the highest and is higher than those of other Fe3+ catalysts, FeCl3 center dot 6H(2)O and FeCl3/SiO2, conventional acid catalysts, Al2O3 and HZSM5, and homogeneous Lewis acid, Sc(OTf)(3). Fe3+-mont exhibits a high turnover numbers (TON = 49,500) and can be recycled without a loss in activity. Acidity of Fe3+-mont, Yb3+-mont and FeCl3/SiO2 was characterized by IR spectroscopy using three probe molecules: pyridine, acetonitrile and acetone. These catalysts dominantly act as Lewis acid, and the Lewis acid strength changes in the order of Fe3+-mont > Yb3+-mont > FeCl3/SiO2, as suggested by acetone adsorption microcalorimety. From the relationship between the activity and the acidic character, factors affecting the catalytic activity for the acetylation are discussed. (C) 2008 Elsevier B.V. All rights reserved.