The mine drainage from mineral and metallurgical processing has complex composition and large amount of water. At present, the effect is not ideal and high cost of heavy metal removal method. In order to solve the problem of heavy metal pollution in mine drainage, a synergistic extraction method has been developed to remove and recover heavy metals from mine drainage, which could be used to the solution with the high acidity and low heavy metal concentration, and inhibit calcium and magnesium ions enter into extractant. A synergistic extractant of Mextral V10–Mextral 973H was obtained for the effective removal of Cu2+, Pb2+, Cd2+ and Zn2+ from the acidic wastewater by the analysis of metal extraction pH isotherms, FT-IR spectrum and UV–vis absorption spectra. The volume ratio of organic phase and water phase (O/A), the saponification rate of Mextral V10 and extracting agent concentration has been studied on the effect of metal ions extraction. The extractability percentage of Cu2+, Cd2+, Zn2+, Pb2+, Mg2+ and Ca2+ were 99.1%±0.1%, 99.9%±0.02%, 99.5%±0.05%, 97.6%±0.03%, 10.11%±0.1% and 18.3%±0.05% respectively after sixth extraction continuously under the optimum experimental conditions of 10vol% (Mextral V10 and Mextral 973H) diluted in Mextral DT100 and Mextral V10:Mextral 973H=1:1, the residual concentration of Cu2+, Zn2+, Cd2+ and Pb2+ in wastewater were 1.720±0.10, 0.256±0.03, 0.054±0.01 and 0.929±0.01 mg/L respectively, which were lower than the maximum allowable emission standard value of class Ⅰ pollutant in GB8978-1996.