The Mg-Al layered-double hydroxides (LDHs) intercalated by three kinds of sulphonato-salen-chromium(III) complexes were prepared and characterized by FTIR, UV-vis, XRD and elemental analysis. It was found that the homogeneous complexes were successfully intercalated into the LDH interlayer via the method of anion exchange followed by coordination with chromium(III) chloride. And the resulting LDH hosted chromium complexes were shown to be effective heterogeneous catalysts for the solvent-free oxidation of benzyl alcohol (BzOH) to benzaldehyde (BzH) using 30% H2O2 as oxidant. Furthermore, owing to the different local environment of the central metal ion chromium(III), the catalyst with the backbone Of o-C6H4 displayed the highest catalytic performance followed by the NH(CH2CH2)(2) with the (CH2)(2) showing the lowest BzH yield. In addition, a tentative mechanism was also discussed. (C) 2007 Elsevier B.V. All rights reserved.