A series of poly(urethane-imide)s with high glass transition temperatures were easily prepared from a commercial nonlinear optical (NLO) chromophore (Disperse Red 19), pyromellitic dianhydride (PMDA), and 2,4-tolylene diisocyanate (TDI). The resulting polymers possessed good solubility and high glass transition temperatures (231-272degreesC) and thermal decomposition temperatures. They exhibited excellent film-forming properties and good-quality films were easily obtained by spin coating. These polymers also possessed a high coefficient of optical nonlinearity with good temporal stability of the dipole orientation.