Fe-PILC samples were synthesized by the reaction between Na+- and/or Ca2+-montmorillonite (Mt) Received 7 March 2008 and base-hydrolyzed solutions of Fe(III) nitrate. Different from the known usual microporous pillared Accepted 30 April 2008 structure, a meso-microporous delaminated structure containing intercalated or pillared fragments was Available online 10 May 2008 found in the respective resulting Fe-intercalated or -pillared clays. XRD patterns of Na+-Mt-based Fe-intercalated/pillared clays show one large d-spacing above 6.4 nm corresponding to the mesoporous Keywords: delaminated part, whereas another d-spacing of ca. 1.5 nm was indicative of the microporous pillared Montmorillonite part. Fe-intercalated/pillared clays based on Ca2+-Mt lead to similar results, but with a d-spacing less Pillared clay Delaminated than 6 nm and a second low intense d-spacing less than 1.5 nm. In the delaminated Fe-intercalated clays, NO3- anions were retained even after thorough washing process. They play as counterions to neuctralize the positive-charged iron aggregates in the delaminated structure, and can be exchanged by heteropolyanions as [PW12O40](3-). The delaminated Fe-pillared clays show good thermal stability at 500 degrees C and exhibit at this temperature dramatically higher specific surface area and porosity than the starting montmorillonites. However, calcination at a higher temperature leads to the formation of nanocrystalline hematite. Air-drying after ethanol extraction (EAD) method has an advantage over air-drying (AD) method in preserving the delaminated structure. (c) 2008 Elsevier Inc. All rights reserved.