Several Mo-containing hydrotalcite-like compounds (HTlcs-Mo) were prepared by different ionic exchange procedures using as parent a synthetic hydrotalcite Mg3Al(OH)8(CO3)(0.5)(.)2H(2)O with a composition similar to the natural occurring mineral. Their physico-chemical properties determined by chemical and TG-DTA analyses, XRD, BET, FTIR, SEM-EDX, DR-UV-vis and Raman spectroscopy, were compared to those of two HT1cs-Mo prepared by direct synthesis at constant pH = 10 and low or respectively high supersaturation. The catalytic activity of these solids towards cyclohexene oxidation with hydrogen peroxide was investigated. The catalytic activity was mainly influenced by the basic properties of the catalysts, which varied depending on the preparation procedure. The best catalysts for hydroperoxidation were found to be those having a low Mo content (about 2.5-2.8%) in the form Of MoO42-species, and higher Mg concentration in the brucite layer. The catalysts containing also Mo7O246- species were more active for epoxidation. (c) 2005 Elsevier B.V. All rights reserved.