The recycling of spent lithium-ion batteries (LIBs) has attracted great attention, mainly because of its significant impact on resource recycling and environmental protection. Currently, the processes involved in recovering valuable metals from spent LIBs have shown remarkable progress, but little attention has been paid to the effective separation of spent cathode and anode materials. Significantly, it not only can reduce the difficulty in the subsequent processing of spent cathode materials, but also contribute to the recovery of graphite. Considering the difference in their chemical properties on the surface, flotation is an effective method to separate materials, owing to its low-cost and eco-friendly characteristics. In this paper, the chemical principles of flotation separation for spent cathodes and materials from spent LIBs is summarized first. Then, the research progress in flotation separation of various spent cathode materials (LiCoO2, LiNixCoyMnzO2, and LiFePO4) and graphite is summarized. Given this, the work is expected to offer the significant reviews and insights about the flotation separation for high-value recycling of spent LIBs.