Simultaneously achieving high Li leaching efficiency and Li/Co selectivity from lithium-ion batteries cathode at mild condition with high sustainability is difficult up to now. To achieve this goal, we here utilize amino acid-based low-melting mixture solvents (LoMMSs) as green solvents. Representative LoMMSs valine:lactic acid (1:12) could leach nearly 100% Li with the high Li/Co selectivity of 48.39 from lithium cobalt oxide (LCO). Effect of temperature, time and leaching agent mass is investigated. Higher temperature continuously increases the Li leaching efficiency, while Co leaching efficiency first increases during the temperature from 25 °C to 60 °C and then decreases at higher temperature. Both Li and Co leaching efficiency when extending the time or adding the leaching agent mass. Mechanism study shows that acid-base interaction and coordination are the main interaction for the high efficiency of metal leach while redox reaction is negligible. This work would provide a useful guide for promoting the industrial application of selectively recycling lithium-ion batteries cathode with high sustainability and low cost.