Poly(amic acid) was synthesized with a low-temperature solution polymerization of 3,3'-dihydroxybenzidine and pyromellitic dianhydride in N,N-dimethylacetamide. The cast films were thermally treated at Various temperatures. The polyimide containing the hydroxyl group was rearranged by decarboxylation, resulting in a fully aromatic polybenzoxazole at temperatures higher than 430 degrees C. These stepwise cyclizations were monitored with elemental analysis, Fourier transform infrared, and nuclear magnetic resonance. Microanalysis results confirmed the chemical compositions of poly(amic acid), polyimide, and polybenzoxazole, respectively. A cyclodehydration from poly(amic acid) to polyimide occurred between 150 and 250 degrees C in differential scanning calorimetry, and a cyclodecarboxylation to polybenzoxazole appeared at 400-500 degrees C. All the samples were stable up to 625 degrees C in nitrogen and displayed excellent thermal stability. Polybenzoxazole showed better thermal stability than polyimide, but polyimide exhibited better mechanical properties than polybenzoxazole. However, polyimide showed a crystalline pattern under a wide-angle X-ray, whereas polybenzoxazole was amorphous. The precursor poly(amic acid) was readily soluble in a variety of solvents, whereas the polyimide and polybenzoxazole were not soluble at all.