The eventual fading and scrapping of lithium (Li)-ion batteries will result in the formation of a huge urban mine of spent batteries. Hydrometallurgy and further extraction/separation are effective ways in which to recover the valuable metal ions from such batteries. Herein, extraction and recovery of spent lithium cobalt oxide (LiCoO₂) battery leach liquors using Cyphos IL-101 is proposed. Based on the optimization of extraction conditions, continuous circulating extraction, and thermodynamic analysis, Cyphos IL-101 effectively extracted cobalt (Co) ions with excellent stability and high extraction capacity (35.25 g/L). The separation factor of Co and Li (β_Co/Li) was 102.11 in 0.5 M HCl at 60 °C under the optimal operation condition. Moreover, an increase in temperature increased Co extraction in the spent Li-ion battery leach liquors. The extractants before and after use were characterized using ultraviolet-visible (UV–Vis) absorption spectra, Fourier transform infrared (FTIR) spectra, and nuclear magnetic resonance (NMR) spectra. The extraction mechanism of cobalt ions by Cyphos IL-101 was suggested as that cobalt transferred to the organic phase from the aqueous phase in the form of [CoCl4]2^-. 90.5% of Co and 86.2% of Li were recovered by precipitation after extraction separation in the forms of cobalt oxalate and lithium carbonate with the purity 87.4% and 74.2%. This suggested method might provide a promising strategy for recycling spent lithium cobalt oxide batteries.