The synthesis and characterization of polyoxovanadate-intercalated MgAl hydrotalcite-like layered double hydroxides (LDH) is described. Seven different methods have been used to intercalate the vanadate anion. These include exchange of the initial carbonate or terephthalate anions, as well as reconstruction of the layered structure from the carbonate form previously calcined at 550-degrees-C-the reconstruction being either directly to the vanadate or indirectly via a terephthalate intermediate. Preswelling with glycerol was also used in some cases. Characterization has been carried out by elemental chemical analysis, powder X-ray diffraction, differential thermal and thermogravimetric analyses, Fourier-transform infrared spectroscopy, transmission electron microscopy, and specific surface area and porosity assessment by nitrogen adsorption at -196-degrees-C. In all cases a layered material containing the [V10O28]6- anion in the interlayer is formed. Direct reconstruction from calcined MgAl LDH with vanadate at pH = 4.5 leads, in addition, to a fibrous material and partial dissolution of magnesium. Experimental results indicate total CO32-/C6H4(COO)22- exchange as well as the absence of glycerol in those cases where it had been used as a preswelling agent. The principal difference between the samples is found within the pore size distribution-a narrow distribution is present in samples prepared via a terephthalate intermediate, while for others the pore size distribution is broader.