Recently, very unfavorable trends of decreasing copper content and increasing complexity of the Polish copper ores as well as lowering quality of final concentrates and metals recovery from concentration plants have been observed. This is also a major problem for the Polish copper smelters, which capabilities are not adapted to the complex and declining deposit conditions. The solution of this problem should be sought in hydrometallurgical methods (Leach-SX-EW). This paper focuses on the role of solvent extraction (SX) in recovering valuable metals from pregnant leach solutions. The problems related to the separation of undesirable and toxic metals are also discussed.