The formation and anion exchange sorption of chloro complex ions can offer a great potential to be utilized for the separation and purification of metals in aqueous solutions. Available stability data were primarily used to estimate the predominance of chloro complex species, indicating the feasibility of such separations. Anion-exchange sorption functions, describing the equilibrium distribution of a number of important elements have been determined by the batch equilibrating method in the practical HCl concentration range. Various oxidation states were stabilized by the addition of appropriate agents. Tendencies in oxidation, complex formation and anion exchange sorption were confirmed by spectrophotometric investigations. Based on the fundamental results, anion exchange processes have been developed for the purification of iron, cobalt, copper and zinc. The efficiency of separation was assessed and the procedure optimized by the analysis of experimental elution curves. Results have demonstrated that by properly controlling the oxidation states and HCl concentrations, practically all the impurities can be eliminated. Computer programs have been developed to estimate complex formation and redox equilibria, to screen and correct analytical data, to determine distribution coefficients and to evaluate efficiencies of separation.