The great geological and soil variation in the state of Minas Gerais, Brazil, indicates the need for regional studies to understand the geochemical background of soils. The Rio Doce Basin became a priority area for geochemical background determination after the rupture of the tailings dam of Fundão in 2015. In this context, the objectives of this study were to propose Reference Values of Soil Quality in the Rio Doce Basin, to define variables that can predict metal(loid) concentrations in the soil, and to examine the correlation between metal(loid) concentrations determined by X-ray fluorescence and by the traditional method. One hundred and seven samples were collected from minimally disturbed areas, representing the main soils and source materials. Metal(loid)s were determined by acid digestion and X-ray fluorescence. Descriptive statistics of the data, as well as the calculation of the Randomized Dependence Coefficient (RDC) and Principal Component Analysis (PCA) were carried out. The soils were found to be acidic, dystrophic with low Mehlich-1 extracted P contents, and have a variable texture. The coefficient of determination ranged from 0.4 to 0.9, suggesting X-ray fluorescence as a promising technique for determining metal(loid) concentrations in soils. The absence of correlation between clay and organic matter contents with metal(loid) concentrations suggests that the latter were inherited exclusively from the parent material, with little influence of pedogenesis. Metal mineralization in the highlands that constitute the topographic drainage divide of the basin increase the reference values of soil quality to higher values than established for the State of Minas Gerais.