We studied the dust fractions of the smelting slag, mine tailings, and soil from the former Ni‐Cu mining and processing district in Selebi‐Phikwe (eastern Botswana). Multi‐method chemical and mineralogical investigations were combined with oral bioaccessibility testing of the fine dust fractions (<48 and <10 μm) in a simulated gastric fluid to assess the potential risk of the intake of metal(loid)s contaminants. The total concentrations of the major contaminants varied significantly (Cu: 301–9,600 mg/kg, Ni: 850–7,000 mg/kg, Co: 48–791 mg/kg) but were generally higher in the finer dust fractions. The highest bioaccessible concentrations of Co, Cu, and Ni were found in the slag and mine tailing dusts, where these metals were mostly bound in sulfides (pentlandite, pyrrhotite, chalcopyrite). On the contrary, the soil dusts exhibited substantially lower bioaccessible fractions of these metals due to their binding in less soluble spinel‐group oxides. The results indicate that slag dusts are assumed to be risk materials, especially when children are considered as a target group. Still, this exposure scenario seems unrealistic due to (a) the fencing of the former mine area and its inaccessibility to the local community and (b) the low proportion of the fine particles in the granulated slag dump and improbability of their transport by wind. The human health risk related to the incidental ingestion of the soil dust, the most accessible to the local population, seems to be quite limited in the Selebi‐Phikwe area, even when a higher dust ingestion rate (280 mg/d) is considered.