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Copper is coated on indium-tin-oxide (ITO) thin film to improve its electrical resistivity. In order to recycle the scrap Cu/ITO thin film, an ionic liquid (1-butyl-3-methyl imidazolium hexafluorophosphate ([C₄mim][PF₆])) containing iodine/iodide (IL-I) was used to extract copper at 303, 343, 413, 374, and 543 K. The extraction efficiency of copper from the scrap Cu/ITO thin film was >99% with IL-I. Using XRD, crystal In₂O₃ was found on the regenerated ITO thin film which had a resistivity similar to that of unused ITO thin film. Using X-ray absorption near edge structural (XANES) spectroscopy, at least two paths for the extraction of copper from the Cu/ITO thin film into IL-I were identified. Path I: Copper is stripped from the scrap Cu/ITO thin film and then interacts with I₃⁻ in the IL-I to form nano CuI. The nano CuI further interacts with I⁻. Path II: Copper interacts with I₃⁻ on the surface of the Cu/ITO thin film to form nano CuI. The nano CuI is further stripped into the IL-I to interact with I⁻. During extraction, the nanoparticle size could be increased in the IL-I by conglomeration due to fewer coordinating anions and decrease in the viscosity of IL-I at high temperatures. Furthermore, nanoparticle growth was affected by [PF₆]⁻ of the IL-I determined via ³¹P NMR.