The cathode materials of spent lithium-ion batteries (LIBs) were recovered via reductive roasting, Na₂CO₃ leaching, and ammonia leaching. The effects of roasting parameters, Na₂CO₃ leaching parameters, and ammonia leaching parameters on the leaching efficiencies of metals were explored. The results show that the mineral phase of spent LIBs is reconstructed during reductive roasting, and more than 99% of Li can be preferentially leached via Na₂CO₃ leaching. Ni (99.7%) and Co (99.9%) can be leached via one-step ammonia leaching, and Mn cannot be leached. Thus, good leaching selectivity is achieved. The kinetic study shows that the leaching of Ni and Co conforms to chemical reaction control.