In the present investigation, novel optically active poly(amid–imide) (PAI)/organoclay (OC)/titanium dioxide (TiO₂) bionanocomposite (BNC) films were prepared by solution intercalation method. These BNCs were synthesized by blending the chiral OC and modified TiO₂ nanoparticles (NPs) with the PAI solution. An optically active PAI containing <sc>l</sc>-phenylalanine amino acid was synthesized via direct polycondensation reaction of N,N'-(pyromellitoyl)-bis-phenylalanine diacid 4 with 4,4'-diaminodiphenylsulfone 5 in the presence of molten tetrabutylammonium bromide as a green solvent. This polymer was end capped with amine end groups of diamine in the final polymerization process. Cloisite Na⁺ and protonated form of <sc>l</sc>-phenylalanine amino acid were used for the preparation of the chiral OC via ion-exchange reaction. The surface of TiO₂ NPs was fictionalized by KH550 (-aminopropyltriethoxyl) coupling agent under ultrasonic irradiation. Finally, PAI/OC/TiO₂ BNC films containing 5 wt% of the OC and 5, 10 and 15 wt% of modified TiO₂ were prepared via solution intercalation technique. The resulting hybrid materials were subjected to Fourier transform infrared spectroscopy, thermogravimetric analysis techniques and x-ray diffraction. The morphology of the obtained materials was examined by transmission electron microscopy and field emission scanning electron microscopy techniques.