An alternative route to prepare polymer-clay nanocomposites using supercritical carbon dioxide (scCO2) is described. The presence of clay nanoparticles significantly influences the morphology, foaming process and crystallization of a polymer when processed in scCO2. Intercalated structures are successfully produced in the presence of scCO2 even when favorable interactions between the polymer and the clay are not present. The effect of scCO2 on the intercalation process is analyzed for a variety of polymer systems both with modified and unmodified clays. By controlling the hydrophilicity of the polymer and clay systems, specific understanding of the effect of scCO2 on the structure and morphology of the nanocomposites is obtained. Experimental results show significant increases in the clays d-spacings for scCO2-treated samples. This behavior is consistent regardless of the nature of the polymer, showing significant amounts of intercalation even in purely hydrophobic polymers.