The recovery of cathode and anode materials plays an important role in the recycling process of spent lithium-ion batteries (LIBs). Organic binders reduce the liberation efficiency and flotation efficiency of electrode materials derived from spent LIBs. In this study, pyrolysis technology is used to improve the recovery of cathode and anode materials from spent LIBs by removing organic binders. Pyrolysis characteristics of organics in electrode materials are investigated, and on this basis, the effects of pyrolysis parameters on the liberation efficiency of electrode materials are studied. Afterwards, flotation technology is used to separate cathode material from anode material. The results indicate that the optimum liberation efficiency of electrode materials is obtained at a pyrolysis temperature of 500 °C, a pyrolysis time of 15 min and a pyrolysis heating rate of 10 °C/min. At this time, the liberation efficiency of cathode materials is 98.23% and the liberation efficiency of anode materials is 98.89%. Phase characteristics of electrode materials cannot be changed under these pyrolysis conditions. Ultrasonic cleaning was used to remove pyrolytic residues to further improve the flotation efficiency of electrode materials. The cathode material grade was up to 93.89% with a recovery of 96.88% in the flotation process.