The role of solvent nature in the liquid phase rearrangement of 1,2-epoxyoctane over Al-TS-1 and Al-MCM-41 catalysts is reported. The main reaction product is the aldehyde, while other rearrangement products, mainly allylic alcohols and diol are obtained. The solvent polarity influences strongly on the activity and product selectivity. The catalytic activity decreases with the increasing of solvent polarity especially for Al-MCM-41 materials. The use of acetonitrile as solvent yields a low conversion of epoxide as a consequence of its basic character. Formation of bulky by-products was detected when dimethylcarbonate was used as solvent over Al-MCM-41. Toluene displays the best catalytic performance in regards to activity and selectivity towards valuable products, with both Al-TS-1 and Al-MCM-41 catalysts, in comparison to those obtained with more polar solvents. (C) 2004 Elsevier B.V All rights reserved.