Copper metallization on polyimide films was carried out via a wet chemical process. This process included the chemical reaction of KOH with PI to form poly(amic acid) (PAA), ion exchange of doped K+ with Cu2+ to form Cu2+-doped PAA, doped Cu2+ reduction by aqueous dimethylamine borane (DMAB) to form copper nanoparticles (CNPs) on PAA, and electroless copper (ELC) deposition catalyzed by CNPs on PAA. An organic additive, namely, bis(3-sulfopropyl)-disulfide (SPS), that can effectively reduce the size of CNPs and significantly enhance the chemical activity of CNPs for ELC deposition was used in this work. For comparison, doped Cu2+ ions in the PAA were also reduced by hydrogen gas at 350 °C. The results show that only aqueous reductants can induce the reduced copper atoms to aggregate on the PAA surface and to form a granular copper layer that acts as a catalyst for the ELC deposition. Mechanisms for the aggregation of copper atoms and for activity enhancement of the CNPs due to SPS addition in the DMAB solution are proposed according to the evidence obtained from Fourier transform infrared spectrometry (FTIR), X-ray photoelectron spectrometry (XPS), field emission scanning electron microscopy (FESEM), cross-sectional transmission electron microscopy (TEM), and atomic force microscopy (AFM). The CNP-coated PAA films and the structures of the ELC deposits were characterized by X-ray diffraction (XRD) and UV-visible spectrophotometry (UV-Vis), respectively.