To study the characteristic of liquid-liquid extraction equilibrium of lithium from brine sources, the complexes formed from tributyl phosphate (TBP) and methyl isobutyl ketone (MIBK) with lithium were investigated using FeCl3 as coextracting agent. Liquid-liquid extraction reaction mechanisms were proposed and the stoichiometry of tetrachloroferrate(III) complex with lithium was obtained by regressing the experimental data. It is found that the stoichiometry of tetrachloroferrate(III) to lithium in the complex is I : 1 with either TBP or MIBK as extractant in kerosene. The stoichiometry of the complex of TBP with Li was 1 : 1 and that of MIBK with Li was 2 : 1. The formed complexes of TBP and MIBK with lithium are determined to be LiFeCl4.TBP and LiFeCl4.2MIBK, respectively, according to the rule of neutralization.