Double-surface-silvered polyimide (PI) films have been successfully fabricated via a direct ion-exchange self-metallization method using silver ammonia complex cation ([Ag(NH3)2]+) as silver resource and bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride/4,4'-oxydianiline (BPADA/ODA)-based poly(amic acid) (PAA) as the PI precursor. The alkaline characteristic of the silver precursor dramatically improves the efficiency of the ion exchange and film metallization process. By using an aqueous [Ag(NH3)2]+ solution with a concentration of only 0.01M and an ion-exchange time of only 5 min, metallized films with desirable performance could be easily obtained by simply heating the silver(I)-doped PAA films to 300 degrees C. The strong hydrolysis effect of the basic [Ag(NH3)2]+ cations on the flexible and acidic BPADA/ODA PAA chains was observed during the ion exchange process by the quantitative evaluation of the mass loss of PAA matrix. Nevertheless, under the present experimental conditions, the final metallized film essentially retained the basic structural, thermal, and mechanical properties of the pristine PI, which make it a truly applicable material. (C) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012