Arenesulfonic modified mesostructured SBA-15 is shown as an active catalyst in the liquid-phase Fries rearrangement of phenyl acetate. The arenesulfonic acid-centers located within the structure of SBA-15 show high catalytic performance as compared to other homogeneous and heterogeneous acid catalysts. This high activity is accompanied with a remarkable stability without leaching of sulphur species during the reaction. Reaction conditions have been investigated in order to optimize production of hydroxyacetophenones. Strong adsorption of reaction products and/or coke deposition on the sulfonic acid sites rapidly deactivates the catalyst. Interestingly, when dichloromethane is used as solvent the deactivation process is slowed down drastically. Finally, this contribution supports a new application of these sulfonated mesostructured materials in the production of fine chemicals. (c) 2005 Elsevier B.V. All rights reserved.