The morphology and thermal stabilization mechanism of polymeric nanocomposites prepared by solution intercalation of linear low density polyethylene (LLDPE) with montmorillonite (MMT), MgAl layered double hydroxide (LDH), and ZnAl LDH have been studied by X-ray diffraction (XRD), transmission electron microscopy (TEM), dynamic Fourier transform infrared (FTIR) spectroscopy, and thermogravimetric analysis (TGA). Both LLDPE/MMT and LLDPE/MgAl LDH nanocomposites exhibit mixed intercalated-exfoliated structures, whereas the LLDPE/ZnAl LDH nanocomposites exhibit completely exfoliated structures because the ZnAl LDH layers can be easily broken during the refluxing process. All nanocomposites show significantly enhanced thermal stability compared with virgin LLDPE due to the increases of the effective activation energy (E-alpha) during degradation process. However, LDHs nanocomposites show much higher thermal degradation temperatures than MMT nanocomposites with the same filler content because they have much higher E-alpha than MMT nanocomposites at the early degradation stage. The data of real time FTIR spectroscopy and morphological evolution reveal a catalytic dehydrogenation effect presents in MMT nanocomposites, which may decrease the E-alpha of degradation and thermal stability of MMT nanocomposites. (c) 2005 Elsevier Ltd. All rights reserved.