Two new samples of poly(amide-imide) (PAI)/ nanocomposites reinforced montmorillonite containing N ,N ′-pyrromelitoyl-bis-l-valine moiety in the main chain were synthesized by a solution intercalation technique. PAI 3 as a source of polymer matrix was synthesized by the direct polycondensation reaction of N ,N ′-pyrromelitoylbis-l-valine 1 with 4,4′-diamino diphenyl ether 2 in the presence of triphenyl phosphite, CaCl2, pyridine and N -methyl-2-pyrrolidone. The morphology and structure of the resulting PAI-nanocomposite films 4a and 4b with 5% and 10% silicate particles were characterized by Fourier transform infrared spectroscopy, X-ray diffraction and scanning electron microscopy. The effect of clay dispersion and the interaction between clay and polymeric chains on the properties of nanocomposites films were investigated by using UV-visible spectroscopy, thermogravimetric analysis and differential scanning calorimetry.