This study is aimed to recover the valuable metal ions from cathode materials of spent Li‒ion batteries (LIBs). Rapid microwave‒assisted dissolution process is investigated here to recover Li and Co from LiCoO₂ of spent LIBs. In the conventional method, about 6 h is required to extract about 90% of Li and Co using a mixture of citric acid (CA) and ascorbic acid (AA) at 80 °C. On the other hand, more than 85% of Li and Co was obtained in about 25 min by microwave (180 W)‒assisted dissolution. The dissolved Co and Li ions were precipitated, selectively: Li as LiHC₂O₄ H₂O or Li₂CO₃ and Co as CoC₂O₄ 2H₂O or Co‒citrate/ascorbate. The Co₃O₄ was formed on heating the Co precipitate at 600 °C for 2 h. It is important to note that LiCoO₂ was re‒synthesized here by thermal decomposition of CoC₂O₄ 2H₂O and LiHC₂O₄ H₂O at 750 °C for about 24 h. Thus, the microwave‒assisted hydrometallurgical method is found to be simple and rapid to recover Li and Co from spent LIBs.