The anionic exchange of the nitrate compensating anions in host Mg/Al LDH by negatively charged [M(Edta)](2-) (M = Ca(2+), Sr(2+), Ba(2+)) guest entities has been performed. The increase from 0.83 nm to 1.5 nm of the d(0 0 3) interlayer distance shows that intercalation has taken place leading to well ordered lamellar materials with 3-9 wt.% of alkaline-earth (AE) cations loading. The basic properties of the M/Mg(Al)O mixed oxides catalysts obtained by thermal decomposition of the [M(Edta)]-Mg/Al LDH precursors have been investigated by TPD of CO(2), FTIR spectroscopy of adsorbed CDCl(3) and catalytic test reaction of 2-methyl-3-butyn-2-ol (MBOH). The AE-containing mixed oxides exhibit higher basicity than Mg(Al)O with, particularly, a large increase of the densities of sites of medium and high strength. Remarkably, the nature of the AE cations allows to finely tune the basicity. All the AE-containing mixed oxides are able to perform the isomerization reaction of 2,3-dimethyl-1-butene (DB-1) into 2,3-dimethyl-2-butene (DB-2), the Ca-containing sample being the most active according to its larger content of strong basic sites. (C) 2009 Elsevier B.V. All rights reserved.