With the continuous expansion of various electronic equipment markets, lithium-ion batteries (LIBs) are widely used in numerous fields. This trend has also brought about the challenge of recycling a growing number of retired and spent LIBs. Although traditional pyrometallurgical and hydrometallurgical recovery technologies have become relatively mature, several issues remain to be addressed. For example, pyrometallurgical processes suffer from relatively low metal recovery efficiencies, while conventional acid/alkali leaching processes often require the addition of extra precipitants to recover certain metals. In this work, a new strategy is proposed for the clean and efficient recovery of Li and Co from spent LiCoO2 cathode materials using a ChCl-OA-H2O deep eutectic solvent (DES). The method involves the selective separation of Co as cobalt oxalate (CoC2O4?2H2O) via preferential precipitation, followed by the direct recovery of Li by adjusting the water content. The entire recovery process requires no additional reagents and is both simple and environmentally friendly. Under optimal conditions (molar ratio 1∶1∶8, solid-liquid ratio 100 g/L), the leaching efficiency of Li can reach 99.4%, and the recovery efficiencies of Li and Co are 88.3% and 97.8%, respectively, demonstrating excellent metal separation and recovery performance. Furthermore, the DES system exhibited good cycling stability, maintaining Li and Co recovery efficiencies of 78.1% and 92.8% after six cycles, which highlights the sustainability and economic potential of the process for practical applications. This study not only provides an efficient and low-pollution technological pathway for battery recycling, but also offers theoretical support and practical evidence for the sustainable cycling of resources, demonstrating significant environmental benefits and promising industrial application potential.