Total concentrations and different forms of antimony (Sb) in soils of Laokuang District (LKQ-1, LKQ-2, LKQ-3), Beikuang District (BKQ-4, BKQ-5, BKQ-6) and Nankuang District (NKQ-7, NKQ-8, NKQ-9, NKQ-10) of Xikuangshan, Hunan province, China were analyzed. The soil Sb concentrations in the whole-ore heap of LKQ-1 and the mining land of NKQ-7 were up to 4258 and 3174 mg/kg respectively, which were both 2000 times above the background soil Sb level in China. In terms of vertical distribution, the Sb concentrations gradually declined with the rise of soil depth. Tessier’s 5-step sequential extraction method showed Sb mainly existed in stable forms (organic-matter-bound form, residual form), and the available form accounted for 18%. The proportions of different forms ranked as residual form >iron/manganese oxides >organic-matter-bound form >carbonate-bound form > water-soluble form. Vegetation affected the form distribution of Sb in a complex way and may increase the bioavailability of Sb, so ecological restoration of Sb can be realized through the absorption by vegetation. Analysis of the geoaccumulation index and the potential ecological risk index showed that Xikuangshan was under extremely severe Sb pollution and very serious potential ecological risk. The Sb mining and smelting activities of humans aggravated local Sb pollution.