A synergistic mixture containing LIX 63 and Versatic 10 with/without TBP was used to simultaneously extract and recover nickel(II) and cobalt(II) from manganese(II), magnesium(II) and calcium(II) in simulated multi-metal wastewater. Stripping kinetics of nickel(II) were improved by adding TBP to the synergistic mixture system containing LIX 63 and Versatic 10. The effects of extraction and stripping conditions on the nickel(II) and cobalt(II) extraction and the removal ratios of impurities were investigated. The results show that when concentrations of LIX 63, Versatic 10 and TBP were correspondingly 0.6, 0.4 and 0.8 mol/L, the respective synergistic extraction coefficient of nickel(II) and cobalt(II) reach to a maximum value of 33.29 and 8.23, and approximately 90% nickel(II) was stripped within 30 min. It is recommended that the metal extraction should be carried out at 40±0.5℃ with equilibrium pH of 4.5, A/O ratio of 1:1 and saponification ratio of 40%. The loaded organic solution was stripped with 1 mol/L H2SO4 solution. Based on the McCabe–Thiele diagrams, through three counter-current extraction stages at an A/O ratio of 1:1, over 98.6% nickel(II) and 99.9% cobalt(II) were correspondingly extracted. Through three counter-current stripping stages at an A/O ratio of 1:10, the loaded strip liquor contained 88.12 g/L nickel(II), 4.52 g/L cobalt(II), 1.21 g/L manganese(II), 0.27 g/L magnesium(II) and below 0.2 mg/L calcium(II).