Despite recent studies have investigated the strong influences of smelting activities on heavy metal contamination in the soil environment, little studies have been conducted on the current information about the potential environmental risks posed by toxic heavy metals in smelting contaminated sites. In the present study, a combination of the bioavailability, speciation, and release kinetics of toxic heavy metals in the indigenous zinc smelting contaminated soil were reliably used as an effective tool to support site risk assessment. The bioavailability results revealed that the bioavailable metal concentrations were intrinsically dependent on the types of chemical extractants. Interestingly, 0.02 mol/L EDTA + 0.5 mol/L CH₃COONH₄ was found to be the best extractant, which extracted 30.21% of Cu, 31.54% of Mn, 2.39% of Ni and 28.89% of Zn, respectively. The sequential extraction results suggested that Cd, Pb, and Zn were the most mobile elements, which would pose the potential risks to the environment. The correlation of metal bioavailability with their fractionation implied that the exchangeable metal fractions were easily extracted by CaCl₂ and Mehlich 1, while the carbonate and organic bound metal fractions could be extracted by EDTA and DTPA with stronger chelating ability. Moreover, the kinetic modeling results suggested that the chemical desorption mechanism might be the major factor controlling heavy metal release. These results could provide some valuable references for the risk assessment and management of heavy metals in the smelting contaminated sites.