Tailings of Pb–Zn ores from Yunnan province of China are of high sulfur content and contains the Pb 0.84% and the Zn 3.67% respectively, it is economic to comprehensive recovery these valuable minerals from the tailings. The results from processing mineralogy of these tailings, the Pb-containing minerals existed mainly as galena and cerusite and the Zn-containing minerals as sphalerite and smithsonite. The laboratory-scale flotation experiment indicated that the valuable minerals were effectively recovered by the differential flotation of sulfide minerals, followed by the desliming and flotation of smithsonite. It is also found that the recovery and grade of Zn concentrate are significantly improved by using the amine collector with the different chain lengths during the roughing and scavenging flotation stage of zinc oxide minerals. Besides, these problems such as a large amount of foam and the difficulty in defoaming existed in the flotation of smithsonite were avoided by using the different chain lengths amine collector. The recovery rate and grade of zinc sulfide concentrates were 23.46% and 13.04%, and the recovery rate and grade of zinc oxide concentrates were 27.86% and 51.69% respectively. The total recovery rate of Zn concentrates was 64.73%. The “Sulphide Ore Priority Flotation-Floating Sulfur Tailings Desliming-Zinc Oxide Flotation” process successfully realized the efficient recovery of lead and zinc minerals in the tailings. In addition, organic amine salts with different carbon chain lengths are used as collectors in the roughing and sweeping stages of zinc oxide, which successfully solves the problems of defoaming difficulties and low concentrate grades that are common in the zinc oxide flotation process. It realizes the efficient recovery of valuable minerals in the tailings, and provides an important basis for the reutilization of this tailings.