A process for efficient separation/recovery of copper involving selective extraction of the copper ion with the aid of an organic extractant from an aqueous chloride solution containing copper and one or more concomitant elements, discharged from an extractive metallurgy of non-ferrous metals or the like, and subsequent stripping. The process of solvent extraction of copper which treats an aqueous chloride solution containing copper and one or more concomitant elements to separate/recover copper, comprising the first step for selective extraction of copper from the aqueous chloride solution by mixing the solution with an extractant of organic solvent composed of tributyl phosphate as the major component after adjusting the solution at an oxidation-reduction potential of 0 to 350 mV (based on an Ag/AgCl electrode), and the second step for stripping of copper by mixing the extractant in which copper is stripped with an aqueous solution.