Mild and green dissolution of lithium cobalt oxide (LCO) with high efficiency is challenging. Here, novel DESs based on poly(ethylene glycol) 200 and p-toluenesulfonic acid monohydrate are designed and found to dissolve LCO with nearly a 100% leaching efficiency at 100 °C within 24 h, which is much higher than the leaching efficiency by DESs in the reported references. The dissolution mechanism investigation shows that the interaction between DESs and LCO is a physical process. This work provides a new strategy for the mild and efficient dissolution of LCO by cheap and green solvents.