Sodium hydroxide solutions are often employed as sterilization agents in the pharmaceutical industry. Here, the chloride content is considered as a critical impurity. In this study, an electrochemical method was developed to remove chloride ions (Cl¯) through the oxidative deposition of AgCl on a Ag anode. The Cl¯ content in the commercially available 50% w/w NaOH solution employed was approximately 100 mg Cl¯/kg NaOH. As the OH¯ content is approximately 18,000 times higher than the Cl¯ content, the formation of AgCl may be expected to be thermodynamically less favorable than the formation of Ag 2 O. However, activation energies for AgCl and Ag 2 O formation have been reported to be approximately 3.8 and 31.2 kJ/mol, respectively, and indicate that AgCl formation is favored. AgCl can be selectively produced by controlling the anode potential. Here, the Cl¯ concentration was reduced to less than 50 mg Cl¯/kg NaOH when an anode potential of 0.18 or 0.19 V vs. Hg/HgO (reference electrode) was applied for one hour at 50°C. XRD analysis and visual monitoring of the Ag anode confirmed the oxidative deposition of AgCl on the anode surface as well as the electrochemical desalination of the concentrated NaOH solution.