LithiumLithium is regarded as a critical raw material globally due to the expanding electric vehicle market. To meet battery supply demands, alternative lithiumLithium sources are being explored, with salt-lake brines emerging as a significant option. Electrodialysis (ED) offers a promising solution, providing high selectivity and productivity with reduced chemical reagent use and energy consumption. This study aims to evaluate the effect of common ions on lithiumLithium separation using ED with monovalent-selective cationic commercial membraneMembranes. Experiments were conducted in a 4-chamber reactor with feed solutions of equimolar chloride salts. The synthetic brine was designed to simulate brines and proof-of-concept experiments were performed. Our comprehensive investigation of various membranesMembranes also provides insights into process integration. Results from the synthetic brine experiments indicated the selectivity order as K > Na > Li >  > Mg > Ca, with the final solution showing a higher ratio of lithiumLithium to divalent ions: Li/Mg and Li/Ca ratios were 5 and 3.5, respectively.