Ultramafic soils are a natural source of metals such as Ni, Co and Cr that can pose ecosystem and human risks. Here, we assessed the environmental, ecological, and human health (carcinogenic and non-carcinogenic) risks from exposure to ultramafic soils through an integrated approach using petrographic and soil mineralogical assessments together with total, available, bioaccessible, and soil fractions analyses of Ni, Co and Cr in ultramafic soils from Brazil. The metal concentrations were similar or up to 5-fold higher for Ni than other studies worldwide in ultramafic soils. Soil sequential extraction showed Co and Ni predominantly bound to Fe and Mn oxides, while Cr was mostly in residual fractions. Medium environmental risks were found for Ni (RAC = 13.0), but no environmental risks were associated with Co and Cr in soils. Ecological risks were high (PERI = 522.8) and significantly high (PERI = 1759.9). Low metal bioaccessibility led to acceptable carcinogenic and non-carcinogenic risks for all routes of human exposure to soil, but consuming vegetables grown in these soils posed unacceptable cancer risks (> 10−3). Our results reinforce the need to monitor ultramafic areas regarding the mobility and availability of metals in the soil to ensure food safety and human health.