An important process in the copper-chlorine water splitting cycle for hydrogen production is electrolysis which occurs after a series of cycle steps that produce the constituents for the anolyte of the electrochemical cell. In this investigation, an anolyte mixture of HCl/CuCl/H2O of varying concentrations is circulated through the electrolyzer to assist in optimizing its performance. It is observed that the concentration and temperature of the anolyte directly affect the process. The efficiency of the electrolyzer is adversely affected, after running a series of experiments, due to copper deposition on the membrane. An important implication of the results is that, to determine the optimal electrolyzer performance, one needs to vary the flow rate and the concentration of anolyte, for a given constant voltage source. In addition, this work demonstrates that aqueous CuCl2 can be recovered from the waste solution exiting the electrolyzer and recycled to the hydrolysis reactor. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.