This study explores enhancing salinity gradient power using 2D materials due to their surface-governed charge. However, achieving high-performing membranes with superior ion selectivity and low ionic resistances remains challenging. To address this issue, Al(OH)₄^- anions were incorporated into graphene oxide membranes to increase their spontaneous negative surface charge. The anions were successfully formed and encapsulated through a reaction with the alumina support under alkaline conditions during the membrane formation. The membranes’ physicochemical properties were analyzed by means of selected characterization techniques. The incorporation of Al(OH)₄^- anions significantly improved permselectivity and ionic resistance, reaching approximately 95% and 2 Ω cm², respectively. A modeling of the system was carried out to further understand the anchoring of these ions within the membrane matrix and their role in boosting the charge of the membrane and, therefore, their electrochemical properties. The study delved into the utilization of GO membranes as monovalent-selective membranes, an approach to boost reverse electrodialysis power densities. The membranes demonstrated impressive selectivity, overcoming 70 folds for divalent cations over K⁺.