In this research work coupled process of electrodialysis and ion exchange resin known as electrodeionization (EDI) and also electrodialysis itself were used in the presence of complexing agents for selective separation of cupper and zinc cations. Experiments were done in two series: in the first series EDI process was used with the help of EDTA as complexing agent whereas in the second series NTA complexing agent was used for ED process. To carry out the experimental work a three compartments electrodialysis cell was designed and built in which its dilute compartment was filled with two different ion exchange resins of gel and macroporous types for the first series of experiments. Using Taghuchi method of design of experiments helped us to reduce the number of experiments and also be able to predict the optimum values of independent parameters and determine the relative importance of these parameters. In this work effect of independent parameters of feed flow rate, applied voltage, ratio of Cu 2+ concentration to that of Zn 2+ as well as pH of the feed solution, and molar ratio of used complexing agent to Cu 2+ concentration on the selective separation factor (RS) were investigated. Obtained results showed a noticeable success of the hybrid method used in this work to separate cations under study selectively. Statistic analysis of the results proved that the molar ratio of the complexing agent had the most effect on the selective separation of cations with contribution of 78.565% in the first series of experiments whereas the most effective independent parameter in the second series of experiments was found to be feed flow rate with contribution of 55.412%. Also it was seen that macroporous ion exchange resin had greater selective separation efficiency in comparison with gel type resin. And finally it was concluded that the best hybrid system for selective separation of cupper and zinc cations was EDI process in the presence of EDTA complexing agent.