The effect of exchanging transition metal ions in the alumina-pillared beidellite/montmorillonite FAZA on the conversion of methanol, ethanol, n-propanol and iso-propanol has been investigated. It is concluded that dehydration/dehydrogenation throughout the series of materials occurs preferentially at the oxidic pillar rather than at the aluminosilicate sheet. The basal structure of the smectite, i.e. whether protons lie inside (montmorillonitic) or outside (beidellitic) the aluminosilicate layers, little influences the reactions. By way of contrast, cation exchange (both single and double) greatly influences both product ratio outcomes and conversions, e.g. Ni-FAZA (FAZA = a Fe2+/Fe3+/alumina-pillared mixed beidellite/montmorillonite) has very acidic centres suppressing MeOH dehydration completely. (C) 2003 Elsevier B.V. All rights reserved.