The synthesis of Ce-MCM-41, Al-MCM-41 and Ce-AI-MCM-41-type mesoporous materials was carried out hydrothermally by refluxing the gel with magnetic stirring under atmospheric pressure for 24-36 h. The samples were characterized thoroughly in order to obtain the structural and textural properties,. which reveal the presence of well-ordered M41 S-type materials. The Ce-MCM-41 samples were used for catalytic acylation of alcohols, thiols, phenols and amines show good activity and selectivity including high chemoselectivity towards selective monofunctional acylation of bifunctional compounds. Quite importantly the acylation of bulky molecules such as cholesterol, ergesterol and P-sitosterol could be achieved using Ce-MCM-41 as solid catalyst. The presence of Ce along with Al in Ce-Al-MCM-41 was found to have synergistic effect as Ce-Al-MCM-41 samples were more active catalysts for alkylation of naphthalene compared to either CeMCM-41 or Al-MCM-41 with comparable Si/Al or Si/Ce molar ratio. (C) 2004 Elsevier B.V. All rights reserved.