A unique class of nanocomposites containing organoclays modified with catalytically active transition metal ions (TMI) and ethylene vinyl acetate (EVA) copolymers was prepared. The morphology, thermal and rheological properties of these nanocomposites were studied by thermal gravimetric analysis (TGA), transmission electron microscopy (TEM), extended X-ray absorption fine structure (EXAFS) spectroscopy, X-ray scattering/diffraction and oscillatory shear rheometry. TMI-modified organoclays were thought to possess pillaring of multivalent TMI in the interlayer silicate gallery, leading to a notable reduction of the interlayer d-spacing. The resulting nanocomposites exhibited significantly improved thermal stability and fire retardation properties, but similar morphology (i.e., an intercalated-exfoliated structure) and theological properties comparable with EVA nanocomposites containing unmodified organoclays. It appears that the compressed organic component in the TMI-modified organoclay can still facilitate the intercalation/exfoliation processes of polymer molecules, especially under extensive shearing conditions. The improved fire retardation in nanocomposites with TMI-modified organoclays can be attributed to enhanced carbonaceous chat formation during combustion, i.e., charring promoted by the presence of catalytically active TMI. (c) 2007 Elsevier Ltd. All rights reserved.