The direct preparation of various aromatic poly(urea‐imide)s (5a₁ –5b₄ ) from N‐[3,5‐bis(trimellitimido)phenyl]phthalimide (1) using diphenylphosphoryl azide (DPPA) was investigated. The polymers were obtained by the conversion of imide ring‐containing diacid 1 to corresponding di(carbonyl azide) 2 with DPPA and then to diisocyanate 3through the Curtius rearrangement of compound 2. This was followed by polyaddition of 3 with two aromatic diamines (4a and 4b). In order to compensate the diisocyanate shortage against the diamines, some excess amounts of the initial triimide‐dicarboxylic acid 1 were used. The molecular weights of the resulting poly(urea‐imide)s were evaluated viscometrically. The poly(urea‐imide)s exhibited an excellent solubility in a variety of polar solvents. The crystallinity nature of the polymers was estimated by means of WXRD. The glass transition temperatures and the 10% wt loss temperatures of the polymers 5a₃ and 5b₃ were determined by DSC and TGA/DTG methods in nitrogen atmosphere, respectively. The transparent films of the resulting polymers were also prepared by casting the solution.