The potential environmental implications of a Pb (Lead)-Zn (Zinc) sulfide tailing impoundment were found to be dependent on its geochemical characteristics. One typical lead-zinc sulfide tailing impoundment was studied. Ten boreholes were set with the grid method and 36 tailings were sampled and tested. According to the results of metal content analysis, the tailing samples contained considerably high contents of heavy metals, ranging from 6.99 to 89.0 mg/kg for Cd, 75.3 to 602 mg/kg for Cu, 0.53% to 2.63% for Pb and 0.30% to 2.54% for Zn. Most of the heavy metals in the sample matrix showed a uniform concentration distribution, except Cd. Cd, Pb, Zn, and Mn were associated with each other, and were considered to be the dominant contributors based on hierarchical cluster analysis. XRD, SEM and XPS were employed for evaluation of the tailing weathering characteristics, confirming that the tailings had undergone intensive weathering. The maximum potential acidity of the tailings reached 244 kg H2SO4/ton; furthermore, the bioavailability of heavy metals like Pb, Cd, Cr, Cu, and Zn was 37.8%, 12.9%, 12.2%, 5.95%, and 5.46% respectively. These metals would be potentially released into drainage by the weathering process. Analysis of a gastrointestinal model showed that Pb, Cr, Ni and Cu contained in the tailings were high-risk metals. Thus, control of the heavy metals’ migration and their environmental risks should be planned from the perspective of geochemistry.