This work is related to the preparation of polymer-clay nanocomposites (PCNs) by the exfoliation-adsorption technique, from atactic poly(methyl methacrylate) (PMMA) in solution, using Bentonite (B) as a layered-silicate natural clay. To optimize the intercalation of B with PMMA, it has been organically modified (OB) with a quaternary ammonium salt that helps the interchange of cations, and thus converting its hydrophilic surface to an organophilic one. An investigation of the morphology and molecular motions or dynamics of the net polymer film as well as the PCN final films was performed by X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), Infra-Red Spectroscopy (IR), Thermally Stimulated Depolarization Currents (TSDC), and Differential Scanning Calorimetry (DSC) techniques. One of our interests was to discuss the solvent influence on the polymeric matrix. Herein, comparative studies of the effects of different solvents on the thermal and dielectric properties of the net PMMA films are reported. Four solvents were used to prepare the films, toluene, dichlorometane, tetrahydrofuran and acetone.