A series of V-doped titania-pillared clay catalysts, characterized by ICP-AES chemical analysis, X-ray diffraction, BET surface area measurement, and ESR spectroscopy, have been tested in the selective catalytic reduction of NO by NH3. An ESR analysis shows that V dopant is anchored to the titania pillars. Vanadyl species with differing degrees of in-plane V-O π-covalent bonding are produced depending on the method of sample preparation. Polymeric V species appear as the V content is increased. Catalytic performance of these systems depends on the method of preparation and on the V content. The best catalyst, converting 90-100% NO in the temperature range 523-623 K, is obtained by exchange of pillared montmorillonite with vanadyl ions, at an extent of exchange below the level where significant amounts of polymeric V species appear. The co-pillared catalyst, containing vanadyl centres characterized by a higher degree of in-plane ncovalent bonding (according to ESR), is less selective than the exchanged samples.