With the intensity of resource scarcities and environmental problems, the disposal and recovery of spent lithium-ion batteries, especially recovery of valuable metals, becomes vital. In this work, a method of co-extracting nickel, cobalt, manganese and being separated from lithium by single-stage solvent extraction is proposed. The extraction and separation process of D2EHPA was studied. The effects of extractant concentration, saponification percentage, extraction time and O:A on the extraction efficiency of D2EHPA were systematically studied. Nearly 100% manganese, 94% cobalt and about 90% nickel were co-extracted and separated from lithium using D2EHPA in kerosene by single-stage extraction. The maximum value of separation factors (βNi/Li, βCo/Li and βMn/Li) was 13.03, 23.42 and 1904.24. The mathematical model of extraction of four ions was developed by combination of Levenberg-Marquardt method and Universal Global Optimization method. The proposed extraction model accurately fits the experimental data and helps to predict the extraction efficiency of each metal under the corresponding conditions.