The efficient recycling of the spent lithium-ion batteries is of great significance for protecting the environment and promoting the sustainable development of the new energy industry. In view of the problems such as high recovery cost and waste gas emissions in the existing combined process, this study proposes a new method for selective lithium extraction from lithium cobaltate cathode material through thermite reduction roasting followed by lime leaching. The thermodynamic analysis of the thermite reduction process of lithium cobaltate is conducted using HSC Chemistry software to determine the feasible reaction path. Subsequently, the influence laws of roasting temperature and the dosage of reducing agent on selective lithium extraction and the phase composition of the roasted product are systematically investigated, and the effects of leaching temperature, leaching time, and the dosage of calcium oxide on selective lithium extraction efficiency are further studied. The roasted products and leaching residues are characterized by techniques such as XRD, SEM-EDS, and XPS. The research results show that the thermite reduction reaction of lithium cobaltate is thermodynamically feasible. Under the optimal roasting conditions of a roasting temperature of 650℃ and an aluminum powder dosage of 25wt%, LiCoO2 is efficiently dissociated and transformed into LiAlO2 and CoO. Subsequently, under the optimal leaching conditions of a leaching temperature of 70℃, a leaching time of 1.0 h, and a calcium oxide dosage twice the theoretical amount, 94.7% of Li can be selectively and efficiently leached. This innovative method exhibits distinct advantages over conventional processes, including zero exhaust gas emissions during thermal treatment, shortened recovery process, low operational costs, and high recovery efficiency of valuable metals. The proposed technique can provide an environmentally friendly and economically feasible solution for the short-process and low-carbon recovery of lithium from spent lithium-ion batteries, and offer a new idea for the sustainable utilization of secondary resources.