Selective extraction of Li from spent lithium-ion batteries (LIBs) is currently a hot topic. However, current research techniques focus on selectively extracting Li from cathode materials, and there are problems with high energy consumption, complex processes, and high difficulty in technical application. And Li in the anode material was ignored. Therefore, this study proposes a technique for selectively extracting Li from anode materials using aqueous solutions. The experimental results show that there is 4.15% Li in the anode material carbon black powder. Under acidic, alkaline, and pure water conditions, the extraction rate of Li from anode materials is greater than 90.00%. Acidic and alkaline conditions can leach heavy metals such as Ni/Co/Mn/Cu, requiring secondary treatment of wastewater, while the concentration of heavy metals leached from water can be directly discharged. When ultrasonic leaching is used for 5−10 min, the leaching rate is greater than 90.00%. When shaking leaching is used for 30−60 min, the leaching rate is greater than 90.00%. When standing leaching is used for 60−120 min, the leaching rate is greater than 90.00%. In the actual production process, suitable enhanced leaching methods can be selected according to different needs. This article may be the first study to propose the selective extraction of Li from anode materials using aqueous solutions.