Copper–silver core–shell nanowires were synthesized using a combination of two methods: electrodeposition in a polycarbonate membrane as a template for the synthesis of a copper core and a galvanic replacement reaction for the elaboration of a silver shell. A comparative study between aqueous and ionic liquid media was performed for the silver shell elaboration. The kinetics of the reaction in both media was monitored by using energy dispersive x-ray spectroscopy. The shape and size of the nanowires were observed by both scanning electron microscopy and transmission electron microscopy. The core–shell structure was determined by electron energy loss spectroscopy analyses for the Cu90Ag10 composition. A homogenous silver shell was formed in aqueous media. Whereas in ionic solvent, well defined silver crystals were obtained at the surface of the nanowires but without a total formation of a silver shell structure.