<p>The selection of extractant plays a pivotal role in the extracting and separating valuable metals from spent ternary batteries. The separation of manganese and cobalt is one of the most critical technical challenges in lithium-ion battery recycling. This is primarily due to their similar chemical properties and comparable extraction pH ranges, which result in a very low separation factor in hydrometallurgical extraction systems. Furthermore, the P204 extractant is highly prone to hydrolysis during long-term operation, leading to decreased stability in the cyclic extraction process. To address these issues, the present research innovatively integrates multi-stage countercurrent extraction technology with optimized extractant combinations and operating parameters to achieve efficient recovery of target metals. Firstly, the waste ternary cathode material is mixed with carbon powder and roasted to convert the valuable metals into a leachable form, followed by sulfuric acid leaching. In the extraction-separation stage, Cyanex 272 is utilized for the preferential selective extraction of manganese. The effects of organic solvent volume fraction, O/A ratio, saponification degree, and extraction time on the extraction efficiency were investigated. P204 is further utilized to remove residual manganese and impurity metals. After that, Cyanex 272 is employed for cobalt/nickel separation, whilst P507 is applied for nickel/lithium separation, achieving efficient stepwise extraction of the target metals. Subsequently, over 98% stripping efficiency for all metals is attained using a sulfuric acid solution. The present process demonstrates two significant advantages. One is the preferential extraction strategy using Cyanex 272 reduces the consumption of P204, thereby lowering operational costs, and the other is the implementation of multi-stage countercurrent extraction improves the overall metal recovery rate of over 95%.</p>