An innovative desalination method called electrosorption or capacitive deionization (CDI) has significant benefits for wastewater treatment. This process is performed by using a carbon fiber electrode as a working electrode to remove hexavalent chromium ions from an aqueous solution. The pH, NaCl concentration, and cell voltage were optimized using the Box-Behnken experimental design (BDD) in response surface methodology (RSM) to study the effects and interactions of selected variables. To attain the relationship between the process variables and chromium removal, the experimental data were subjected to an analysis of variance and fitted with a quadratic model. The optimum conditions to remove Cr(VI) ions were: pH of 2, a cell voltage of 4.3V, and NaCl concentration of 1.4 g/L. This study demonstrated that the carbon fiber electrode was very efficient in Cr(VI) ions removal and the BBD methodology was a practical and effective strategy for predicting the results of various experimental conditions during a CDI process for the removal of chromium ions.