In this work, new optically active poly(amide-imide)s (PAIs) having bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic diimide groups were prepared by the reaction of N,N'-(bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic)bis-l-phenyl alanine (4) as a diacid monomer with various readily available aromatic diamines. Triphenyl phosphite (TPP)/pyridine (Py) in the presence of calcium chloride (CaCl2) and N-methyl-2-pyrrolidone (NMP) were successfully applied for direct polycondensation. The diacid (4) was synthesized by the condensation reaction of bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (1) with l-phenyl alanine (2) in acetic acid solution. The resulting new polymers were obtained in good yields, inherent viscosities ranging between 0.29 and 0.48 dLg(-1) and were characterized with elemental analysis, FT-IR, H-1-NMR spectroscopy, specific rotation, and thermal gravimetric analysis (TGA, DTG) techniques. Thermogravimetric analysis indicated that the residual weight percent of polymers at 600 A degrees C was between 53.80 and 56.21%, which show these are moderately thermally stable. In addition because of existence of chiral center and optical activity of these polymers, they have potential to be used as chiral stationary phase in chromatography technique for the separation of racemic mixtures.