This article compares two exfoliation options of multilayered silicate, one considering the action of shear stress and temperature during melt compounding and another taking into account the action of the thermo-mechanical pretreatment of multilayered silicate in a plasticizer common to the starch and polyvinyl alcohol (PVOH), the two polymers from the compound. Increasing the action time of the shear stress and temperature during melt compounding proved to be an ineffective method for silicate exfoliation following the high degradability of starch and PVOH under thermo-mechanical conditions and the loss of hydration of the multilayered silicate under thermo-mechanical conditions. The obtained results prove that, by pretreating before embedding into the desired starch-PVOH matrix, it was possible to cancel the electrostatic attractions between the component lamellae of a multilayered silicate. During melt compounding with the two polymers, new attractions between the obtained lamellae and the polar groups of each polymer from the blend were settled, and so, without the usage of a liquid plasticizer, exfoliated intercalated nanocomposites were achieved. The improved properties and the practical importance of the new nanocomposites regards the obtaining of a non-degradable material that has a white color, better elastic properties and thermal stability, and a higher dissipation capacity of deformation energy.