Abstract: Lithium recovery from spent lithium-ion batteries (LIBs) have attracted extensive attention due to the skyrocketing price of lithium. The medium-temperature carbon reduction roasting was proposed to preferential selective extraction of lithium from spent LiCoO₂ (LCO) cathodes to overcome the incomplete recovery and loss of lithium during the recycling process. The LCO layered structure was destroyed and lithium was completely converted into water-soluble Li₂CO₃ under a suitable temperature to control the reduced state of the cobalt oxide. The Co metal agglomerates generated during medium-temperature carbon reduction roasting were broken by wet grinding and ultrasonic crushing to release the entrained lithium. The results showed that 99.10% of the whole lithium could be recovered as Li₂CO₃ with a purity of 99.55%. This work provided a new perspective on the preferentially selective extraction of lithium from spent lithium batteries.