Diamines, namely, 1,4-bis(4-amino-2-phenylphenoxy) benzene (1) and 4,4 0 -bis(4-amino-2-phenylphenoxy) biphenyl (2), were synthesized from 4-fluoro-3-phenyl nitrobenzene. Two series of polyimides were synthesized from these diamines with nine types of dianhydrides by a conventional two-step procedure that included ring-opening polymerization in N-methyl-2-pyrrolidone and subsequent thermal cyclic dehydration. The polyimides were characterized by x-ray diffraction, differential scanning calorimetry, thermogravimetry and dynamic mechanical analysis. The polyimides from 1 and 2 had a glass transition temperature in the range of 221-254 C and 222-271 C, respectively, and all the polymers were amorphous. The structure-property relationships of these polyimides were examined and compared with those of the previously prepared analogous polyimides from the bis(4-amino-2-biphenyl)ether (3). Water absorption and dielectric constants (e) of the polyimides were compared and discussed on the basis of imide content per repeating unit.