The invention discloses a method for effectively separating valence substances from a waste lithium battery. The method comprises the steps of classifying the waste lithium battery according to different types, discharging the waste lithium battery in discharging equipment, and disassembling to obtain an internal battery cell and an outer package aluminum shell; smashing the battery cell, adding an organic solvent for immersion, and performing filtering and oil removal; adding water for stirring, allowing the mixture to stand, and separating a separator; performing wet ball-milling on filtered powder, adding water for dilution, performing flotation, and separating high-purity graphite and aluminum powder; and changing concentration of paste and a flotation condition, and performing secondary flotation so that flotation upper-layer positive powder and flotation lower-layer copper powder can be obtained. The separation method has the characteristics of simplicity, low energy consumption, small environmental pollution, low production intensity, good separation effect and high recycle ratio and has relatively good production benefit, and each valence substance in the waste lithium battery can be effectively separated.