This study uses the solvent extraction method to separate and recover aluminum and nickel from the alkali leaching residue of spent hydrogeneration catalysts. It compared and analyzed the extraction efficiency of P204 (Di (2?ethylhexyl) phosphate) and P507 (2?ethylhexylphosphonic acid mono?2?ethylhexyl ester) and investigated the effects of initial pH, the volume fraction of P204, the saponification rate of P204, and the ratio of V(org)/V(aq) on the extraction of aluminum and nickel in the P204 extraction system. The experimental results show that P204 demonstrates better extraction performance than P507 in the separation of aluminum and nickel. Under a concentration of 35% and saponification ratio of 30% of P204, initial pH of 2.75, and V(org)/V(aq) of 3∶1, the extraction rate of aluminum and nickel is 96.45% and 2.77%, respectively. In the two?stage countercurrent extraction process, the extraction rate of aluminum can reach more than 99.50% while that of nickel is below 3.60%. The loaded organic solvent was stripped at 60 ℃ and V(org)/V(aq) =2∶1 for 20 minutes by 6 mol/L HCl solution, and the stripping efficiency of aluminum in the organic phase is 98.04%. Thus, the separation of aluminum and nickel in spent catalysts can be effectively realized.