Another technique for desalination, known as membrane capacitive deionization (MCDI), has been investigated as an alternative. This approach has the potential to lower the voltage that is required, in addition to improving the ability to renew the electrodes. In this study, the desalination effectiveness of capacitive deionization (CDI) was compared to that of MCDI, employing newly produced cellulose acetate ion exchange membranes (IEMs), which were utilized for the very first time in MCDI. As expected, the salt adsorption and charge efficiency of MCDI were shown to be higher than those of CDI. Despite this, the unique electrosorption behavior of the former reveals that ion transport via the IEMs is a crucial rate-controlling step in the desalination process. We monitored the concentration of salt in the CDI and MCDI effluent streams, but we also evaluated the pH of the effluent stream in each of these systems and investigated the factors that may have caused these shifts. The significant change in pH that takes place during one adsorption and desorption cycle in CDI (pH range: 2.3–11.6) may cause problems in feed water that already contains components that are prone to scaling. In the case of MCDI, the fall in pH was only slightly more noticeable. Based on these findings, it appears that CDI and MCDI are promising new desalination techniques that has the potential to be more ecologically friendly and efficient than conventional methods of desalination. MCDI has some advantages over CDI in its higher salt removal efficiency, faster regeneration, and longer lifetime, but it is also more expensive and complex. The best choice for a particular application will depend on the specific requirements.