A series of poly(arylene imino)s (PAI) with high molecular weights and small polydispersity indices have been synthesized by the condensation polymerization of different diiodobenzenes with aromatic primary diiminos via two different methods. Their structures were characterized by means of FT-IR, 1 H NMR spectroscopy and elemental analysis. DSC and TG measurements show that the polymers possess high glass transition temperatures (T g ＞ 150 ℃) and good thermal stability with high decomposition temperatures (T D ＞400 ℃). These novel polymers also exhibit good solubility in organic solvents.