A new series of diamines, 4-aryl-2,6 bis(4-amino phenyl)pyridine, bearing bulky aromatic-type pendant groups were prepared and reacted with three different dianhydrides. The best conditions of polymerization and imidization were obtained via a study of model compound. All polyimides showed excellent thermal stability, and those based on hexafluoroisopropylidene-2.2-bis(phthalic-dianhydride) had very good solubility in polar aprotic solvents.