ABSTRACTIn the preparation of polymer/montmorillonite (MMT) nanocomposites, the commonly used compatibilizers (cations of long carbon‐chain alkyl ammonium salts) present the drawback of a poor thermal stability. During bulk processing of nanocomposites elevated temperatures are usually required and, if processing temperature is close to decomposition temperature of the surfactant, decomposition will occur altering the interface between filler and polymer. To solve this problem, organically modified MMTs with thermally stable imidazolium surfactants have been prepared. A series of nanocomposites were obtained by dispersing o‐MMT in poly(methyl methacryate) (PMMA) matrix via an in situ free radical polymerization. The nanocomposites were characterized by X‐ray diffraction, transmission electron microscopy, gel permeation chromatography, thermogravimetric analysis, dynamic mechanical analysis, and nanoindentation measurements. The results showed that nanocomposite thermal stability depended on both the kind of used surfactant and degree of exfoliation. Under the same values of molecular weight, the nanocomposites containing imidazolium cations showed a better thermal stability with respect to the nanocomposite obtained using a standard alkylammonium surfactant. Dynamic mechanical and Nanoindentation measurements showed an improvement of mechanical properties, such as modulus and hardness, with respect to pure PMMA. Solution blending treatments on these nanocomposites led to obtaining of further improvement of the thermal performance. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41393.