Vermiculites have the potential to serve as effective catalysts if pillared with Al, but their high charge presents an obstacle to the pillaring process. The purpose of this study was to submit natural vermiculite to thermal treatments in the presence of water vapor in order to effect a reduction in the global negative charge and thereby to enhance its susceptibility to pillaring. The process of charge reduction in vermiculite under the conditions selected involved the extraction of 25% of IVAl accompanied by the extraction of structural Mg and charge-compensating cations (Ca2+, Na+, and K+). The results indicate a reduction of 35% in the global negative charge in vermiculite by the end of the treatment. Some of the VIAl content was not removed during acid washing, and probably remained in the solid in structural positions in the octahedral sheet.