<p>With the development of new energy sources, the demand for lithium in the world is increasing, and the exploitation and utilization of lithium resources has become a urgent need. In the process of lithium salt production, a large amount of lithium precipitation mother liquor will be produced, which contains a large number of lithium resources. Due to its high Na⁺/Li⁺ ratio, it is difficult to extract Li⁺. The purpose of this paper is to study the performance of electrochemical lithium extraction method based on LiFePO₄-Pb oxide system in lithium precipitation mother liquor. The specific capacity of the system can reach 120 mAh·g^− 1 at 0.1&#xa0;C. The system has good cycling performance in both high and low concentration Li₂SO₄ solution. The coulomb efficiency is basically above 90% in the rate test.It still has high selectivity for Li⁺ in lithium precipitation mother liquor with a Na⁺/Li⁺ratio of up to 10:1 (molar ratio), the concentration of Li⁺ in the mother liquor decreased by 21.12 mM and the concentration of Li⁺ in the extracting solution increased by 20.61 mM after three cycles. The average inserted capacity of Li⁺ was 20.1&#xa0;mg/g and the extracted capacity was 19.6&#xa0;mg/g. The separation coefficient of Li/Na is as high as 237.91. It can extract Li⁺ efficiently and has good recycling performance. It provides an advanced method for extracting Li⁺ from lithium precipitation mother liquor.</p>