This paper describes a new approach for the preparation of polyamic acid (PAA) composites containing Ag and Au nanoparticles. The composite film of PAA and metal particles were obtained upon electrodeposition of a PAA solution containing gold or silver salts with subsequent thermal treatment, while imidization to polyimide is prevented. The structural characterization of the films is provided by H-1 NMR and Fourier transform infrared spectroscopy (FTIR), while the presence of metallic nanoparticles within the polymeric matrix was confirmed by scanning electron microscopy (SEM), cyclic voltammetry (CV), energy-dispersive X-ray analysis (EDX), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). This approach utilizes the unique reactivity of PAA by preventing the cyclization of the reactive soluble intermediate into polyimides at low temperature to design polymer-assisted nanostructured materials. The ability to prevent the cyclization process should enable the design of a new class of electrode materials by use of thermal reduction and/or electrodeposition.