The pre-concentration of electrode material of spent lithium-ion battery has great significance on the resource utilization and environmental protection. The feasibility of separation of graphite and LiCoO₂ based on density difference using the enhanced gravity concentrator was verified in this paper. Combustion characteristics of LiCoO₂ and graphite were used to propose a simple evaluation index of separation efficiency. Separation tests were carried out to specify the influence of operating parameters on the separation efficiency. Moreover, the effect of particle size on the separation performance was studied. Combustion characteristics results showed that mass loss of graphite was much greater than that of LiCoO₂. Thus, mass loss were used to evaluate the purity of product. Effective separation of graphite and LiCoO₂ was achieved by the enhanced centrifugal separator. Separation results showed that increasing centrifugal force decreased the overflow yield and increased the graphite content of the overflow stream. In addition, yield of overflow grew an increase in fluidization water pressure, while the purity of graphite in overflow decreased. The effect of particle size on the separation efficiency was also significant, the separation efficiency decreased with the decreasing of particle size.