There is increasing interest in using ionic liquids (ILs) as solvents for polymerization processes. The use of an inexpensive and readily available IL such as tetrabutylammonium bromide (TBAB) as a solvent for clean synthesis and catalytic processes is becoming widely recognized and accepted. This article reports an extension of a microwave method, describing the synthesis of optically active polyamides (PAs) in TBAB. Polycondensation reactions of diacid 5-(3-methyl-2-phthalimidylpentanoylamino) isophthalic acid with different diisocyanates such as 4, 4′-methylenebis(phenyl isocyanate), toluylene-2,4-diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate were carried out in the presence of TBAB as a molten salt under microwave irradiation and with a conventional heating method, and they were compared with polymerizations in a traditional solvent such as 1-methyl-2-pyrrolidone. A series of optically active PAs with high yields and inherent viscosities ranging from 0.20 to 0.60 dL/g were obtained. These PAs were characterized with Fourier transform infrared spectroscopy, specific rotation measurements, 1H-NMR, elemental analysis, thermogravimetric analysis, and differential scanning calorimetry. All data agreed with the proposed structures. Some physical properties and structural characterizations of these PAs are reported.