Solvent extraction has been employed to purify media simulating chloride-leaching solutions resulting from complex sulfide concentrate processing, and cyclic voltammetry (CV) has been chosen to characterize those hydrometallurgical aqueous phases. The possibilities of the CV technique were investigated by the evaluation of the adequacy of a specific organic extractant, triisobutylphosphine sulfide, aimed to efficiently and selectively extract silver from a complex chloride medium, additionally containing tenfold to 40-fold molar concentrations of iron, copper and lead. The influence of the oxidation state of the metallic ions present in the feed solution, namely Cu(II) and Cu(I), is considered. The possibilities of CV analysis for the characterization of stripping solutions are also illustrated.