Polyimide is well-known high-performance material, but it is difficult to bind nanoparticles on polyimide surface. In this paper, surface bound silver nanoparticles on polyimide were prepared by a surface modification method. The approach involved an alkali hydrolyzation of polyimide and ion-exchange reaction leading to silver doped in polyimide. The silver ions were reduced during thermally re-imidization of the hydrolyzed polyimide and agglomerated to silver nanoparticles on polyimide surface. The detailed reaction progress and resulted silver nanoparticles were characterized by FTIR, EDX, XRD, AFM and TEM. The surface bound silver nanoparticles allowed for interfacing of the wide range of organic and biological thiol-containing molecules and could directly serve as catalyst site for electroless metal plating. Satisfactory electroless copper patterns were obtained on this substrate using alkanethiol SAM on silver particles as a simple photoresist. (C) 2004 Elsevier B.V. All rights reserved.