This work was to investigate the lithium ion fractionation from various binary cation systems at various operating temperatures by electrodialysis (ED) with monovalent selective ion exchange membranes (usually called selective-electrodialysis, S-ED). Then a ternary cation system was selected to verify the results obtained from the binary cation systems. In Li+-Mn+ (Mn+: Na+, K+, Mg2+, Ca2+) brines containing only one kind of anion-Cl-, higher efficient recovery of lithium was obtained at higher temperature than at lower one, and the separation coefficients (FM-Li ) at the same lithium recovery ratio were found to be changed slightly with temperature ranging from 10 degrees C to 30 degrees C. The results indicate the relationship between transport enhancement/interionic separation effects and temperature could be preliminarily expressed by Arrhenius-type equation. Moreover, the pore size of membrane and the cationic hydration number were analyzed with temperature increase, and then that FM-Li had little variation caused by temperature was explained. It should attribute to the swelling of membrane and a small reduction of cationic hydration numbers. Further verification was done in Li+-Na+-Mg2+ cation system, and the same results were obtained. The investigation experimentally demonstrates that S-ED technology is feasible for separating and recovering lithium from brines in different regions with different environment temperatures. (C) 2018 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.