To improve the extraction yield of polyprenols (PPs), the novel -complexing extractant that consisted of 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6) containing AgBF4 was used to extract PPs from the extracts of Ginkgo leaves. The results showed that the extraction rate of PPs reached 93.13% at 23C, while the initial concentration of PPs in n-hexane of 2g/l, silver iron concentration in the extractant of 0.02 mol/L, the volume ratio of material solution to extractant of 1:1 and extraction of 2 h. Compared with previous methanol aqueous AgNO3 extractant, [BMIM]PF6-AgBF4 extractant showed much lower silver iron concentration and significant shorter operation times. When the extractent was recycle three times, the average extraction rate was 91.21%, showing no obvious decline.