At present, solvent extraction is an effective method to remove heavy metals from soil, which has certain practical significance. The physical properties such as density, viscosity and conductivity of NADESs with different proportions synthesized based on the double solid components of glycolic acid (GA) and L-proline (L-PRO) and the physical properties of NADESs aqueous solution at the lowest eutectic point (3:1) were studied. The extraction effect of NADESs on soil heavy metal Pb2+ under different conditions was studied. The results showed that under the conditions of atmospheric pressure of 101.33 kPa, the lowest eutectic melting point, DESs concentration of 0.6 mol·L−1, extraction temperature of 313.15 K and extraction time of 4 h, the extraction rate of Pb2+ by NADESs was 95.28%. In addition, the internal structure of DESs was characterized by IR and NMR, which indicated that intermolecular hydrogen bonds were formed. and the interaction between DESs and Pb2+ was analyzed by quantum chemical calculation, which showed that the hydroxyl group of GA was more likely to form coordination bond with Pb2+, and chelation occurred between them. This kind of DESs provides a new idea for the removal of heavy metals in soil.