Selective extraction of Zn from blast furnace dust can be achieved by the ammonium sulfate roasting-water leaching process. An innovative method for effective separation of Zn, Fe, and Mn from roasting-water leaching solution of blast-furnace dust by precipitation-solvent extraction process is proposed in this research. The Fe of leaching solution was selectively converted into FePO4·2H2O precipitate by using Na2HPO4 as precipitant. The precipitation efficiency of Fe reached 99.17%, while that of Zn was only 0.20% under the solution pH of 2.2, molar ratio of Na2HPO4 to Fe of 1.2 : 1, reaction temperature of 30 ℃, and reaction time of 50 min. The zinc in the filtrate was extracted with Cyanex 302, and Zn (99.94%) was extracted through two-stage countercurrent extraction under initial pH of 3.4, Cyanex 302 concentration of 25%, and O/A of 2 : 1. Subsequently, Zn (99.96%) of the organic phase was stripped using 0.75 mol/L sulfuric acid by one-stage countercurrent stripping. Furthermore, according to thermodynamic calculation, it is proved that extracting Zn from sulfuric acid solution with Cyanex 302 is an exothermic reaction. The proposed process flowsheet may be used to efficiently recover Zn and Fe from blast-furnace dust.