Aromatic polyimides were synthesized from 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6F-OH diamine) and different aromatic dianhydrides by a one-step high-temperature polycondensation, or by a two-step procedure using either thermal or chemical imidization of poly(amic acids), PAA. The obtained poly imides were compared in terms of their chemical structure, molecular weight, mechanical and thermal properties. The reaction of 6F-OH diamine with different aromatic dianhydrides in amide solvents at room temperature resulted in the formation of PAA with moderate molecular weight (eta(inh) less than or equal to 0.7 g/dL). The thermal imidization of these PAAs led to brittle hydroxy polyimides (PI-6F-OH). In contrast, chemical imidization of similar PAAs in acetic anhydride and pyridine brought about flexible self-supporting polyimide films. The FTIR analysis indicated that the latter process was accompanied by an esterification of the OH groups in the diamine moieties, resulting in the formation of the polymers with side act!tate groups (PI-6F-Ac). The high molecular weight hydroxy polyimides, suitable for preparation of films with good tensile properties, were synthesized by a one-step high-temperature polycondensation in phenolic solvents. All obtained polyimides were well soluble in con!mon organic solvents. The highest solubility was observed for PI-GF-Ac. It was found by means of FTIR and TGA that the polyimides with the R group (R = OH or acetate) in orto position to the nitrogen atom in the diamine moiety underwent a rearrangement to benzoxazoles above 300 degrees C. The starting temperature and conversion of this rearrangement reaction were controlled by the type of R group. The imide-to-benzoxazole rearrangement shifted to lower temperatures, and higher conversion was encountered for the polyimides with side acetate group, PI-6F-Ac, obtained by chemical imidization.