Selective leaching of Li from spent LIBs thermally pretreated by pyrolysis and incineration between 400 and 700 °C for 30, 60, and 90 min followed by water leaching at high temperature and high L/S ratio was examined. During the thermal pretreatment Li₂CO₃ and LiF were leached. Along with Li salts, AlF₃ was also found to be leached with an efficiency not higher than 3.5%. The time of thermal pretreatment did not have a significant effect on Li leaching efficiency. The leaching efficiency of Li was higher with a higher L/S ratio. At a higher leaching temperature (80 °C), the leaching of Li was higher due to an increase in the solubility of present Li salts. The highest Li leaching efficiency of nearly 60% was observed from the sample pyrolyzed at 700 °C for 60 min under the leaching condition L/S ratio of 20:1 mL g⁻¹ at 80 °C for 3 h. Furthermore, the use of an excess of 10% of carbon in a form of graphite during the thermal treatment did not improve the leaching efficiency of Li.