The equilibria and speciation in the solvent extraction of LiCl by nonamethyl-14-crown-4 ether in 1-octanol have been determined by use of ion chromatography (IC) and inductively coupled plasma (ICP) analyses, equilibrium modeling with the program SXLSQI, and Li-7 NMR measurements, SXLSQI modeling of the extraction data indicates the formation of a 1:1 metal:crown complex in the organic phase, The complex apparently exists as an ion-pair Li(crown)Cl, which partially dissociates to the complex cation Li(crown)(+) and free chloride anion Cl-. Extraction of LiCl by 1-octanol to give the organic-phase ion-pair LiCl and its dissociated ions Li+ and Cl- must be included in the data analysis. Li-7 NMR measurements verify the existence of free and crown-complexed lithium species in 1-octanol, and the measurements quantitatively agree with results from the SXLSQI model.