A facile synthesis of an optically active di-isocyanate containing alkylene groups and a preformed imide structure is described. Polycondensation reactions of the prepared di-isocyanate with pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, and hexafluoroisopropylidene diphthalic anhydride resulted in the preparation of optically active, thermally stable polyimides. The prepared monomer and polymers were characterized by conventional methods. Optical and physical properties of the polymers including thermal stability, thermal behavior, solution viscosity, and solubility behavior were studied. (C) 2001 John Wiley & Sons, Inc.