Thermal curing of the (4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionato)silver(I)-containing poly(amic acid) formed from 3,3′,4,4′-benzophenone tetracarboxylic acid dianhydride (BTDA) and 4,4′-oxydianiline (4,4′-ODA) in dimethylacetamide gives both polyimide films via cyclodehydration and reduction of silver(I) to the native metal. Silver(0) migrates to the surface resulting in surface metallized composite films, which can have excellent reflectivity, but do not exhibit surface electrical conductivity. The films retain mechanical and thermal properties similar to those of the parent polyimide. X-ray diffraction shows crystalline face-centered-cubic silver in the films after thermal curing. Microscopy data show that the surface particle sizes are in the range of approximately 50–100 nm. Significant silver remains in the bulk of the polyimide film with varying particles sizes generally less than approximately 15 nm. The interior of the metallized films is not electrically conducting. Films were characterized by x-ray diffraction, differential scanning calorimetry, thermal gravimetric analysis, x-ray photoelectron spectroscopy, transmission electron microscopy, scanning electron microscopy, and mechanical measurements.