A novel lead and bismuth deep-separation extraction-stripping system is proposed for the leaching solution of molybdenite-bismuthinite mixed ore, which creates perfect conditions for the preparation of high-purity bismuth-based materials. Based on the activity and ionic strength theories, the forms of bismuth and lead present in the solution were predicted according to the thermodynamic models of different systems. The results showed that N235 + 2-octyl alcohol + kerosene formed a synergistic extraction system, which realized the synergistic extraction of bismuth, iron and lead with solvent extraction ratios of 98.74 %, 9.34 % and 46.24 %, respectively. In addition, the FTIR spectra of bismuth and lead before and after extraction were recorded to better understand the extraction and vaporization mechanisms. When stripping with water, the stripping ratios of iron and lead were 99.87 % and 99.74 %, respectively, while the loss ratio of bismuth was only 0.01 %. In conclusion, this study will be a key link in the comprehensive recycling process of bismuth resources.