Novel nanocomposite films based on amylose (AM) and Fe3+–montmorillonite (Fe3+–MMT) in the matrix of poly(vinyl pyrrolidone) (PVP) were fabricated using a solution casting method. X-ray diffraction indicated that an ion exchange process occurred between Fe3+–MMT and PVP/AM. Thermogravimetric analysis and differential scanning calorimetry results hinted to PVP/AM films forming a more stable network through the dispersion of Fe3+ cations. An increase in the loading of Fe3+–MMT improved the hydrophilic properties of PVP/AM films, which lead to the high degree of resistance against the water absorption. Mechanical properties of PVP/AM films influenced by the uniform dispersion of Fe3+–MMT in the polymer network established strong covalent interactions between PVP/AM and Fe3+–MMT. This interaction not only improved the mechanical properties of the films, but also enhanced the thermal stability of them through the facilitation of the MMT dispersion within the polymer matrix.