The effect of deposited vanadium on the thermal destruction of ultra stable Y (USY) zeolite in the presence of sodium ions and steam was investigated by solid-state NMR. When USY zeolite containing few sodium ions was heated in a dry atmosphere, Si-OH groups, which corresponded to defect sites, and strong adsorption sites were formed by the dealumination. The former mainly caused an increase in the mean void volume per supercage and the latter originated from cationic extra framework Al in the supercages. Furthermore, in the dry atmosphere, the sodium ions inhibited the dealumination; the effect of the deposited vanadium on the structural change was not large. After the heat treatment in 100% steam, in case of USY zeolite containing few sodium ions, the crystallinity and the supercage structure hardly changed although the dealumination occurred remarkably. This process did not depend on the deposited vanadium. Data suggested that the heat treatment in 100% steam causes the framework stabilization. In case of USY zeolite containing a number of sodium ions, the synergistic effect between a few deposited vanadium ions and the sodium ions on the framework destruction in 100% steam was tremendous. We propose that the deposited vanadium functions as vanadic acid and catalyzes the conversion of the sodium ions into NaOH. Thus, an increase in the NaOH content promotes the 'dissolution' of the zeolite crystal, i.e. the framework destruction. In addition, when the sample containing both a few vanadium ions and a number of sodium ions was heated in 100% steam, the supercage was plugged partially. We believe that the blockage compounds in the supercage are sodium vanadates. (C) 2003 Elsevier Science B.V. All rights reserved.