Environmental availability and profile characteristics of arsenic (As), cadmium (Cd), lead (Pb) and zinc (Zn) were studied in contaminated vegetable soils from the Pb/Zn mining and smelting areas in Hunan Province of China, and the potential environmental risks of these metals were also assessed. The results show that the concentrations of As, Cd, Pb and Zn in vegetable soils are higher than the levels of Soil Environmental Quality of China (GB15618-1995). The mobility of metals in soil profiles is mainly characterized by the low pH and organic matter content of soil. The major part of As, Cd, Pb and Zn is restricted to the upper soils and the contamination of these metals in soils is significantly influenced by the long-term Pb/Zn mining and smelting activities. Based on the results from the BCR sequential extraction, the fraction of Cd in the soil profiles is predominantly existed in the acid-extractable form and the large amount of Pb is closely associated with reducible fraction. The environmental availability of Cd and Pb is predominantly higher than that of As and Zn in the soil profiles, suggesting Cd and Pb have more huge potential risk for human health and surrounding environment.