Metal-ion-induced crosslinking of poly(amic acid) (PAA) was observed in the incorporation of silver ions into PAA through ion exchange. Studies on the interaction of silver ions with 3,3',4,4'-benzophenone-tetracarboxylic acid/4,4'-oxidianiline (BTDA/ODA)-based PAA suggest that the ion exchange reactions between poly(amic acid) and silver ions are not so simple as what we generally believed. It involves not only the formation of silver carboxylate but also the generation of diversified silver chemical entities arising from the strong chemical bonding of metal ions with the functional groups, Such as carbonyl groups and amide groups, in the polymer chain, which are Suggested to be responsible for the crosslinking behavior. Moreover, silver ions loaded into the film are readily self-reduced and provides us a convenient route to disperse very small metal nanoparticles into the polymeric matrix. Meanwhile, strong accelerating effect of silver ions was observed on the hydrolysis of PAA molecules and the characterization results indicate that about 14-16 wt% precursors were dissolved during the ion exchange in the aqueous silver ion solutions. Fortunately, it is found that the metal-ion-induced crosslinking structure formed in the silver-doped film has helped to prevent the damaging effect of silver ions and the essential Structural features of PAA were retained in the remaining polymer matrix. (C) 2008 Elsevier Ltd. All rights reserved.