Poly(N-phenylphenyleneamine)s have been synthesized by a modified Ullmann condensation. The number average molecular weights of the oligomers synthesized were in the range of 1350-1700 with a molecular weight distribution of 1.6. The oligomers are thermally stable. Their glass transition temperatures range from 166 to 182 degreesC as characterized by differential scanning calorimetry. The electron photoemission spectra of the oligomers have been recorded and the ionization potentials of 5.2-5.4 eV have been established. (C) 2003 Elsevier Science B.V. All rights reserved.