Abstract When vanadyl naphthanate solutions in toluene are used to V-contaminate rectorite pillared with alumina clusters, V migration from the pillared clay microporous structure to the outer surface occurs during the thermal treatments used in catalyst preparation. The presence of V on the clay catalyst surface can be inferred from atomic force microscopy (AFM) images showing a marked decrease in surface roughness resulting from the presence of vanadia. AFM images show what are believed to be islands as well as stacks of vanadia layers on the clay surface. Irrespective of the thermal and hydrothermal treatments used to prepare these catalysts, atomic scale details of V-contaminated clay samples retain the surface parameters characteristic of the silicate layers in smectites. These results suggest that V on the clay surface is present as VO groups attached to the three basal oxygens of the SiO 4 units that form the clay silicate layers. These VO units form an hexagonal arrangement of white spots having next neighbor ( d c) and lateral distance ( d l) of 5.2 Å and 9.1 Å, respectively.