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.