A series of new optically active and thermally stable poly(amide-imide)s (6a-e) were synthesized by direct polycondensation reaction of N,N'-(bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic)-bis-L-leucine (4) with various aromatic diamines using polar aproptic solvents such as N-methyl-2-pyrolidone (NMP). In this technique triphenylphosphite (TPP) and pyridine were used as condensing agents to form poly(amide-imide) through the N-phosphonium salts of pyridine. The resulting new polymers (6a-e) were obtained in high yields, with inherent viscosities between 0.21 and 0.32 dL/g, and were characterized by (1)H-NMR, FTIR spectroscopy, elemental analysis, specific rotation, gel permeation chromatography (GPC), and thermogravimetric analysis (TGA and DTG). The solubility of these polymers was good in polar aprotic solvents such as N,N-dimethyl acetamide (DMAc), N,N-dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), NMP (N-methyl-2-pyrolidone), and solvents such as sulfuric acid. The diimide-diacide 4 was prepared by condensing reaction of bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride 1 with L-leucine 2 in the acetic acid solution.