We investigate the multilayered structures of poly(ethylene)oxide/montmorillonite nanocomposite films made from solution. The shear orientation of a polymer-clay network in solution combined with simultaneous solvent evaporation leads to supramolecular multilayer formation in the film. The resulting films have highly ordered structures with sheet-like multilayers on the micrometer length scale. The polymer covered clay platelets were found to orient in interconnected blob-like chains and layers on the nanometer length scale. Inside the blobs, scattering experiments indicate the polymer covered and stacked clay platelets oriented in the plane of the film. The polymer is found to be partially crystalline although this is not visible by optical microscopy. Atomic force microscopy suggests that the excess polymer, which is not directly adsorbed to the clay, is wrapped around the stacked platelets building blobs and the polymer also interconnects the polymer-clay layers. Overall our results suggest the re-intercalation of clay platelets in films made from exfoliated polymer-clay solutions as well as the supramolecular order and hierarchical structuring on the nanometer, via micrometer to the centimeter length scale.