Procedures leading to preparation of vanadium-doped alumina-pillared montmorillonites are described and physico-chemical characterization (chemical analysis, XRD, BET, DTA and ESR) of the products is provided. Results show that introduction of vanadium into the pillared montmorillonites leads to a rigid association of the dopant with pillars, irrespective of the mode of preparation. The XRD and DTA data indicate that oligocationic species formed during "co-pillaring" differ structurally from the standard Al₁₃ ions. It is argued that blocking of the interlayer may occur on "co-pillaring" due to the more dense packing of oligocations, brought about by a decrease in their average charge.