The growing demand for lithium necessitates the development of an efficient process to recover it from three kinds of solutions, namely brines as well as acid and alkaline leach liquors of primary and secondary resources. Therefore, the separation of lithium(I) from these solutions by solvent extraction was reviewed in this paper. Lithium ions in brines are concentrated by removing other metal salts by crystallization with solar evaporation. In the case of ores and secondary resources, roasting followed by acid/alkaline leaching is generally employed to dissolve the lithium. Since the compositions of brines, alkaline and acid solutions are different, different commercial extractants are employed to separate and recover lithium. The selective extraction of Li(I) over other metals from brines or alkaline solutions is accomplished using acidic extractants, their mixture with neutral extractants, and neutral extractants mixed with chelating extractants in the presence of ferric chloride (FeCl₃). Among these systems, tri-n-butyl phosphate (TBP)- methyl isobutyl ketone (MIBK)-FeCl₃ and tri-n-octyl phosphine oxide (TOPO)- benzoyltrifluoroacetone (HBTA) are considered to be promising for the selective extraction and recovery of Li(I) from brines and alkaline solutions. By contrast, in the acid leaching solutions of secondary resources, divalent and trivalent metal cations are selectively extracted by acidic extractants, leaving Li(I) in the raffinate. Therefore, bis-2,4,4-trimethyl pentyl phosphinic acid (Cyanex 272) and its mixtures are suggested for the extraction of metal ions other than Li(I).