Quaternary ammonium salts of sulfonated polystyrene (SPS) were used as compatibilizers for melt intercalation of PS and pristine Na-montmorillonite. Tetra-octyl ammonium SPS and tetra-decyl ammonium SPS ionomeric compatibilizers produced significant exfoliation and a homogeneous dispersion of the polymer–clay nanocomposites. Wide angle X-ray diffraction and transmission electron microscopy were primarily used to characterize the morphology of the nanocomposites. Image analysis was used to measure the percentage exfoliation. Exfoliation increased with the increasing length of the alkyl chain of the ammonium counter-ion of the SPS ionomer. The nanocomposites containing ionomers exhibited higher storage moduli compared to nanocomposites without the compatibilizer.