Pure chitosan and carbon nanotube (CNT)/chitosan nanocomposite films were fabricated via a sublimation-drying process at -196 A degrees C, during which polymeric repulsion generates unique pores with multi-layered structures. The films were then transformed into multi-layered and vertically aligned multi-layered (VAM) structures by compression. Due to the cross-linking between layers, the films prepared at -196 A degrees C showed significantly better mechanical properties than the films prepared at -78 and -20 A degrees C. Furthermore, a peculiar phenomenon was observed in that pure chitosan which exhibited better mechanical properties than the nanocomposites. To explain these results, we suggest a model in which the VAM structure supports more load than the CNT fillers.