The large-scale use of electric vehicles produced massive discarded lithium-ion batteries, containing many recyclable valuable metals and toxic and harmful substances. Biodegradable and recyclable deep eutectic solvent (DES) is considered a green recycling technology for spent LIBs. Herein, we proposed a microwave-enhanced approach to shorten the leaching time in the urea/lactic acid: choline chloride: ethylene glycol DES system. The dipole moments induced by urea or lactic acid on LiCoO2 surface increased over two orders of magnitude under the high electric field. Because of this, over 90 % of Li and Co can be fast leached at 4 min and 160 W in the urea/lactic acid: choline chloride: ethylene glycol DES system. Meanwhile, we established two models to explain the leaching mechanism of metal ions from their leaching kinetics and micro-level behavior, and named them dot-etching and layer-peeling processes, respectively. By further analyzing, we found that the dot-etching can be attributed to the synergistic effect of reduction and coordination, which caused the surface of leaching residues porous. The layer-peeling process depends on neutralization, and the leaching residues had a smooth surface in this process. This work highlights the effect of microwave-enhanced strategy and DES surface chemistry on spent electrode materials recovery.