Double-surface-silvered polyimide films have been successfully fabricated using silver ammonia complex cation ([Ag(NH3)(2)](+)) as the silver precursor and 3,3',4,4'-benzophenonetetracarboxylic dianhydride/4,4'oxidianile- (BTDA/ODA-) based poly(amic acid),(PAA) as the polyimide precursor via a direct ion-exchange self-metallization technique. The-process has been clarified to involve the loading of silver(l) into PAA via ion exchange, the thermally induced reduction of silver(l) to silver(0) and the concomitant imidization of PAA to polyimide upon thermal treatment, the subsequent silver-catalyzed and oxygen-assisted decomposition of the polyimide overlayer, and the self-accelerated aggregation of silver clusters on the film surface to produce well-defined surface silver layers. By employing [Ag(NH3)(2)](+) solution with a concentration of only 0.01 M and an ion-exchange time of no more than 10 min, the controlled formation of highly reflective and conductive silver surfaces upon thermal treatment at 300 degrees C for less than 4.5 h indicates that the present work provides an efficient route and an effacious silver species for polyimide surface metallization. Although the alkaline characteristics of [Ag(NH3)(2)](+) have a strong hydrolysis effect on the polyimide precursor chains, the final metallized films retain the key mechanical and thermal properties of the pure polyimide. Films were characterized by ATR-FTIR, XPS, ICP-AES, SEM, TEM, DSC, TGA, reflectivity, conductivity, and mechanical measurements.