Sedum alfredii Hance is a newly reported zinc (Zn) and cadmium (Cd) hyperaccumulator native to China. In this study, four populations of S. alfredii were collected from Yejiwei (YJW), Jinchuantang (JCT) and Qiaokou (QK) lead (Pb)/Zn mines located in Hunan Province as well as Quzhou (QZ) Pb/Zn mine located in Zhejiang Province for exploring the intraspecies difference of this plant in metal accumulation. Although they grew in the Pb/Zn spoils with relatively similar levels of Zn, Cd and Pb, remarkable differences among the four populations in tissue heavy metal concentrations were observed. The shoot Zn concentration of QZ population (11,116 mg/kg) was highest and nearly five times higher than that of the JCT population (1930 mg/kg). Furthermore, the shoot Cd concentration observed in the QZ population (1090 mg/kg) was also highest and 144 times higher than that found in the JCT population (7.5 mg/kg). As for Pb concentrations in the shoot of different populations, a fourfold difference between the highest and the lowest was also found. Such difference on metal accumulation was population-specific and may be significantly explained by differences in the soil properties such as pH, organic matter (OM), and electrical conductivity (EC). Taking biomass and metal concentration in plants into consideration, the QZ, YJW and QK populations may have high potential for Zn phytoremediation, the QZ population may have the highest potential in Cd phytoremediation, and the QK population may be the most useful in Pb phytoremediation.