Recycling spent Li-ion batteries (LIBs) is paramount to pursuing resource efficiency and environmental sustainability. This study introduces a synergistic approach for selectively leaching and separating strategic metals from waste LIBs, representing a more efficient alternative to traditional single-acid-based leaching methods. The research also thoroughly analyzes diverse extraction parameters, aiming to achieve clean metal separation through synergistic concepts rather than single-phase extraction. The outcome of this study is developing a comprehensive downstream process, advancing the cause of sustainable waste management in the LIB industry. Under specific conditions with 0.6 mol/L total acid content (0.5 mol/L tartaric acid + 0.1 mol/L ascorbic acid), 99.9% cobalt and 100% lithium were effectively leached. The subsequent extraction process achieved a clean separation, with 48.3% of cobalt extracted using a mixture of 0.1 mol/L Alamine-336−Cyanex-272 (A-336−Cy-272) from the leach liquor with no coextraction of lithium, and this efficiency was improved to 67.3% by adjusting the pH from 2.44 to 7.5. However, it is worth noting that increasing the extractant concentration led to an antagonistic effect. To further enhance cobalt enrichment in the organic phase, the McCabe−Thiele plot method was recommended, employing saponified Cy-272. Moreover, the regeneration of saponified Cy-272 was investigated, and the stripped solution was processed with NaOH to form Co(OH) 2 , subsequently converting it into cobalt oxide (Co 3 O 4 ) through calcination.