Thermally stable organically modified clays based on 1,3-didecyl-2-methylimidazolium (IM2C10) and 1-hexadecyl-2,3-dimethyl-imidazolium (IMC16) were used to prepare poly(ethylene naphthalate) (PEN)/montmorillonite (MMT) nanocomposites via a melt intercalation process. Examination by X-ray diffraction and transmission electron microscopy indicates that an intercalated nanocomposite was formed with IMC16-MMT, while unmodified MMT (Na-MMT) and IM2C10-MMT are generally incompatible with PEN. Thermogravimetric analysis reveals that the peak derivative weight loss temperature of the intercalated PEN/IMC16-MMT was more than 10 "C higher compared to neat PEN, PEN/Na-MMT, or PEN/IM2C10-MMT. Dynamic mechanical analysis also showed that a more significant improvement of the storage modulus was achieved in the better dispersed PEN/IMC16-MMT. The effect of annealing on the dynamic storage modulus of the hybrids is also investigated.