Coal is a primary energy source in the world. Potentially toxic metals (PTMs) emission from coal mining and combustion are posing a serious public health concern. In order to quantify and evaluate the effect of PTMs on children’s health, the concentrations of 12 PTMs (As, Co, Cr, Cu, Mn, Ni, Pb, Sr, Zn, Ca, Fe, and Mg) bound in urban soil and street dust are determined and blood lead levels of these PTMs in 229 children (0–6 years old) are collected from the coal mining city of Yulin, China. In vitro pulmonary bioaccessibilities of PTMs are evaluated by artificial lysosomal fluid and Gamble’s solution, and gastrointestinal bioaccessibilities by the unified BAGRE method (UBM); correlations between chemical speciation of PTMs and their bioaccessibility are examined, and children’s (0–6 years old) health risks are systematically studied. Similar distribution levels of PTMs are found in soils and dusts, with the most polluted metals being Co, Sr, Ca and Pb. All PTMs (except Cr, Fe) are from the considerable artificial lysosomal fluid extraction both in soil and dust, while Ca and Co are favorably extracted in gastro and intestinal phases than others. Significant correlations are observed between the bioaccessibilities (lung and gastrointestinal) and Fe/Mn hydroxide-bound and carbonate-bound phases, which are key factors influencing and determining PTMs’ bioaccessibility. Blood lead levels for children (0–6 years old) are 27.47 (21.65, 33.30) for 0–1 year olds, 32.29 (26.39, 38.19) for 1–2 year olds, 36.99 (28.16, 45.81) for 2–3 year olds,30.79 (22.56, 39.01) for 3–4 year olds, 27.12 (17.31, 36.93) for 4–5 year olds, 34.59 (24.22, 44.97) for 5–6 year olds and 37.83 (24.15, 51.51) μg/L for 6–7 year olds, respectively, with 3.93%, 3.49%, 4.80%, 2.62%, 1.31%, 1.75% and 1.31% exceeding 50 μg/L, respectively. This indicates that the blood lead levels elevate for 1–2 year and 5–6 year old groups, which should be paid more attention. Although the non-carcinogenic and carcinogenic risks of most PTMs are under the acceptable level, the higher carcinogenic risk of Ni and non-carcinogenic risk of
Pb should be monitored continuously. We suggest that further actions will be taken to reduce PTMs exposure for children through sustainable clean and ecological energy technology for coal mining, especially for those infants of 1–2 years old.