A variety of materials with different structural features and acid properties, including amorphous, mesostructured and zeolitic catalysts have been tested in the liquid-phase rearrangement of 1,2-epoxyoctane. The structure and acid strength of the catalysts influence strongly on the activity and product selectivity. The main rearrangement products are the aldehyde, allylic alcohols and diol. Acid sites in the amorphous materials show a poor catalytic activity. Al-TS-1 and Al-Ti-beta, zeolites with medium aluminium content, lead to significant activities and selectivities towards both the aldehyde and the octenols in comparison to those obtained with other zeolitic materials tested. Aluminium-containing mesostructured materials present much higher activities than amorphous and zeolitic catalysts. Al-MCM-41 synthesised by a sol-gel method at room temperature yielded selectivities to octaldehyde and octen-l-ols of 40.6 and 44.7%, respectively, with a high catalyst activity (TOF of ca. 30.5). (C) 2004 Elsevier B.V. All rights reserved.