The ion-exchange method for the purification of primary coolant has been used broadly in PWR(pressurized water reactor)-type nuclear power plants due to its high decontamination efficiency, simple system, and easy operation. However, its non-selective removal of metal and non-radionuclides shortens its life, resulting in the generation of a large amount of waste ion-exchange resin. In this study, the feasibility of electrodeionization (EDI) was investigated for the purification of primary cooling water using synthetic solutions under various experimental conditions as an alternative method for the ion exchange. The results shows that as the feed flow-rate increased, the removal efficiency increased and the power consumption decreased. The removal rate was observed as a 1000 decontamination factor(DF) at a nearly constant level. For the synthetic solution of 3 ppm TDS (Total Dissolved Solid), the power consumption was 40.3 mWh/L at 2.0 L/min of feed flow rate. The higher removal rate of metal species and lower power consumption were obtained with greater resin volume per diluting compartment. However, the flow rate of the EDI process decreased with the elapsed time because of the hydrodynamic resistivity of resin itself and resin fouling by suspended solids. Thus, the ion-exchange resin was replaced by an ion-conducting spacer in order to overcome the drawback. The system equipped with the ion-conducting spacer resolved the problem of the decreasing flow rate but showed a lower efficiency in terms of the power consumption, the removal rate of metal species and current efficiency. In the repeated batch operation, it was found that the removal efficiency of metal species was stably maintained at DF 1000.