Two novel optically active poly(amide-imide)s (PAI)s were prepared by the direct polycondensation of diamine, 3,5-diamino-N-(4-(5-(4,5-diphenyl-1H-imidazol-2-yl)furan-2-yl)phenyl)benzamide with two optically active dicarboxylic acids such as N,N′-(pyromellitoyl)-bis-l-phenylalanine and N,N′-(4,4′-carbonyldiphthaloyl)-bis-l-phenylalanine in molten tetrabutylammonium bromide (TBAB) as a green medium with triphenyl phosphite as condensing agent. The diamine was synthesized via the direct condensation of 2-[5-(4-aminophenyl)furan-2-yl]-4,5-diphenyl-1H-imidazole with 3,5-dinitrobenzoyl chloride and following reduction in the dinitro compound. The resulting PAIs had inherent viscosities of 0.38 and 0.35 dL g−1. The PAIs were dissolved in polar organic solvents, such as NMP, DMAc, DMSO and DMF at room temperature. These polymers were solution-cast from DMAc solution into transparent, flexible and tough films. Wide-angle X-ray measurement exhibited that the PAIs were amorphous. These PAIs had 10% weight loss temperatures of 427 and 440 °C under nitrogen atmosphere. The polymer films had a tensile strength of 102 and 108 MPa and a tensile modulus of 2.2 and 2.3 GPa. The adsorption capability of one of the PAIs for removal Cu2+ from aqueous solutions was tested at pH 5.